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Sample records for metal carbonyl complexes

  1. 31P{1H}NMR and carbonyl force constants of unsymmetrical bidentate phosphine complexes of group (VI) metal carbonyls

    NASA Astrophysics Data System (ADS)

    Jesu Raj, Joe Gerald; Pathak, Devendra Deo; Kapoor, Pramesh N.

    2015-05-01

    In our present work we report synthesis of an unsymmetrical diphos ligand, 1-diphenylphosphino-2-di-m-tolylphosphinoethane and its coordinate complexes with group (VI) metal carbonyls such as Cr(CO)6 Mo(CO)6 and W(CO)6. The synthesized ligand and its complexes have been completely characterized by elemental analyses, FTIR, 1HNMR, 31P{1H}NMR and FAB mass spectrometry methods. Special emphasis has been given to calculations of carbonyl force constants. Based on the spectroscopic evidences it has been confirmed that these metal carbonyl complexes with the ditertiary phosphine ligand showed cis geometry in their molecular structure.

  2. Chirp-driven vibrational distribution in transition metal carbonyl complexes.

    PubMed

    Gollub, C; Korff, B M R; Kompa, K L; de Vivie-Riedle, R

    2007-01-21

    In this theoretical study vibrational ladder climbing in transition metal carbonyl complexes, as a possible means to initialize chemical ground state reactions, and the resulting vibrational population distribution using chirped mid-infrared femtosecond laser pulses is investigated. Our model system is MnBr(CO)(5), a strong IR-absorber within an experimentally easily accessible wavelength region. Special emphasis is put on the perturbation due to additional vibrational modes, especially on one, which allows dissociation at low energies. The related potential energy surface for the three representative modes is calculated, whereon quantum dynamics calculations, including the laser-molecule interaction, are performed. No significant coupling could be detected, neither in the bound, nor in the dissociative region. Contrarily, we found a dynamical barrier even for energies high above the dissociation limit. Different vibrational population distributions after the laser excitation of the CO stretching mode could be generated in dependence of the chirp parameters. Based on these findings we simulated the laser excitation corresponding to an experiment by M. Joffre et al., Proc. Natl. Acad. Ssi. U. S. A., 2004, 101(36), 13216-13220, where coherent vibrational ladder climbing in carboxyhemoglobin was demonstrated and we could offer an explanation for an open question, concerning the interpretation of the spectroscopic data.

  3. THE METAL CARBONYLS.

    PubMed

    Blanchard, A A

    1941-10-03

    When the metal carbonyls were first discovered, their properties were startling because they seemed to violate nearly all the previously recognized generalizations of chemistry. Even to-day the existence of the carbonyls is not particularly emphasized in elementary courses of chemistry because it is rather hard to reconcile them with the first presentations of the generalizations of chemistry. Nevertheless, as the student progresses deeper into the knowledge of chemistry it becomes desirable to include the knowledge of the carbonyls both because they become more comprehensible when viewed in the light of Werner's system of coordination and because they themselves contribute to the comprehension of the Werner theory. As long ago as 1931, Reiff in his discussion of cobalt nitrosyl carbonyl recognized the correlation between the effective atomic number and the volatility of carbonyls. A more recent study of charged Werner coordination complexes, that is, of complex ions, has shown a similar role of the effective atomic number. We are standing on fairly firm ground when we point out the correlation between E.A.N. and the volatility of the carbonyl complexes and the existence of complex ions. Be it noted that we have made no postulates as to the arrangement of the electrons in quantum levels. In the inert gases the outer principal quantum group is supposed always to contain eight electrons. In the carbonyls and other Werner complexes there is no compelling reason to suppose that the electrons in the coordinating layer, be this layer of eight, ten, twelve or sixteen electrons, are not all at the same energy level. Although we have confined our discussion almost exclusively to the property of volatility, the carbonyls are very interesting from the standpoint of several other properties, for example, magnetic susceptibility and dielectric constant. Enthusiasts in the interpretation of such properties try to draw conclusions as to the condition of the electrons, sometimes

  4. Direct observation of a bent carbonyl ligand in a 19-electron transition metal complex.

    PubMed

    Lomont, Justin P; Nguyen, Son C; Harris, Charles B

    2013-03-21

    The photochemistry of [CpRu(CO)2]2 in P(OMe)3/CH2Cl2 solution has been studied using picosecond time-resolved infrared (TRIR) spectroscopy. Photolysis at 400 nm leads to the formation of 17-electron CpRu(CO)2(•) radicals, which react on the picosecond time scale to form 19-electron CpRu(CO)2P(OMe)3(•) adducts. The TRIR spectra of this adduct display an unusually low CO stretching frequency for the antisymmetric CO stretching mode, suggesting that one carbonyl ligand adopts a bent configuration to avoid a 19-electron count at the metal center. This spectral assignment is supported by analogous experiments on [CpFe(CO)2]2 in the same solvent, combined with DFT studies on the structures of the 19-electron adducts. The DFT results predict a bent CO ligand in CpRu(CO)2P(OMe)3(•), whereas approximately linear Fe-C-O bond angles are predicted for CpFe(CO)2P(OMe)3(•). The observation of a bent CO ligand in the 19-electron ruthenium adduct is a surprising result, and it provides new insight into the solution-phase behavior of 19-electron complexes. TRIR spectra were also collected for [CpRu(CO)2]2 in neat CH2Cl2, and it is interesting to note that no singly bridged [CpRu(CO)]2(μ-CO) photoproduct was observed to form following 400- or 267-nm excitation, despite previous observations of this species on longer time scales.

  5. Carbonyl substitution chemistry of some trimetallic transition metal cluster complexes with polyfunctional ligands

    SciTech Connect

    Byrne, Lindsay T.; Hondow, Nicole S.; Koutsantonis, George A.; Skelton, Brian W.; Torabi, A. Asgar; White, Allan H.; Wild, S. Bruce

    2008-11-03

    The trimetallic clusters [Ru{sub 3}(CO){sub 10}(dppm)], [Ru{sub 3}(CO){sub 12}] and [RuCo{sub 2}(CO){sub 11}] react with a number of multifunctional secondary phosphine and tertiary arsine ligands to give products consequent on carbonyl substitution and, in the case of the secondary phosphines, PH activation. The reaction with the unresolved mixed P/S donor, 1-phenylphosphino-2-thio(ethane), HSCH{sub 2}CH{sub 2}PHPh ({double_bond}LH{sub 2}), gave two products under various conditions which have been characterized by spectroscopic and crystallographic means. These two complexes [Ru{sub 3}({mu}dppm)(H)(CO){sub 7}(LH)] and [Ru{sub 3}({mu}-dppm)(H)(CO){sub 8}(LH)Ru{sub 3}({mu}-dppm)(CO){sub 9}], show the versatility of the ligand, with it chelating in the former and bridging two Ru{sub 3} units in the latter. The stereogenic centres in the molecules gave rise to complicated spectroscopic data which are consistent with the presence of diastereoisomers. In the case of [Ru{sub 3}(CO){sub 12}] the reaction with LH{sub 2} gave a poor yield of a tetranuclear butterfly cluster, [Ru{sub 4}(CO){sub 10}(L){sub 2}], in which two of the ligands bridge opposite hinge wingtip bonds of the cluster. A related ligand, HSCH{sub 2}CH{sub 2}AsMe(C{sub 6}H{sub 4}CH{sub 2}OMe), reacted with [RuCo{sub 2}(CO){sub 11}] to give a low yield of the heterobimetallic Ru-Co adduct, [RuCo(CO){sub 6}(SCH{sub 2}CH{sub 2}AsMe(C{sub 6}H{sub 4}CH{sub 2}OMe))], which appears to be the only one of its type so far structurally characterized. The secondary phosphine, HPMe(C{sub 6}H{sub 4}(CH{sub 2}OMe)) and its oxide HP(O)Me(C{sub 6}H{sub 4}(CH{sub 2}OMe)) also react with the cluster [Ru{sub 3}(CO){sub 10}(dppm)] to give carbonyl substitution products, [Ru{sub 3}(CO){sub 5}(dppm)({mu}{sub 2}-PMe(C{sub 6}H{sub 4}CH{sub 2}OMe)){sub 4}], and [Ru{sub 3}H(CO){sub 7}(dppm)({mu}{sub 2},{eta}{sup 1}P({double_bond}O)Me(C{sub 6}H{sub 4}CH{sub 2}OMe))]. The former consists of an open Ru{sub 3} triangle with four

  6. Density functional calculation of core-electron binding energies of transition metal carbonyl and nitrosyl complexes

    NASA Astrophysics Data System (ADS)

    Hu, Ching-Han; Chong, Delano P.

    1996-11-01

    Our recent procedure of the unrestricted generalized transition state (uGTS) model for density functional calculations of core-electron binding energies has been applied to seven carbonyl and nitrosyl inorganic complexes: Fe(CO) 5, Ni(CO) 4, Mn(CO) 4NO, Co(CO) 3NO, Fe(CO) 2(NO) 2, Mn(NO) 3CO and Cr(NO) 4. The exchange-correlation potential is based on a combined functional of Becke's exchange (B88) and Perdew's correlation (P86). The cc-pVTZ basis set was used for the calculation of neutral molecules, while for the partial cation created in the uGTS approach we scaled the cc-pVTZ basis set using a procedure based on Clementi and Raimondi's rules for atomic screening. The average absolute deviation of the calculated core-electron binding energy from experiment is 0.28 eV.

  7. Laser-driven localization of collective CO vibrations in metal-carbonyl complexes

    NASA Astrophysics Data System (ADS)

    Lisaj, Mateusz; Kühn, Oliver

    2014-11-01

    Using the example of a cobalt dicarbonyl complex it is shown that two perpendicular linearly polarized IR laser pulses can be used to trigger an excitation of the delocalized CO stretching modes, which corresponds to an alternating localization of the vibration within one CO bond. The switching time for localization in either of the two bonds is determined by the energy gap between the symmetric and asymmetric fundamental transition frequencies. The phase of the oscillation between the two local bond excitations can be tuned by the relative phase of the two pulses. The extend of control of bond localization is limited by the anharmonicity of the potential energy surfaces leading to wave packet dispersion. This prevents such a simple pulse scheme from being used for laser-driven bond breaking in the considered example.

  8. Design strategies to improve the sensitivity of photoactive metal carbonyl complexes (photoCORMs) to visible light and their potential as CO-donors to biological targets.

    PubMed

    Chakraborty, Indranil; Carrington, Samantha J; Mascharak, Pradip K

    2014-08-19

    The recent surprising discovery of the beneficial effects of carbon monoxide (CO) in mammalian physiology has drawn attention toward site-specific delivery of CO to biological targets. To avoid difficulties in handling of this noxious gas in hospital settings, researchers have focused their attention on metal carbonyl complexes as CO-releasing molecules (CORMs). Because further control of such CO delivery through light-triggering can be achieved with photoactive metal carbonyl complexes (photoCORMs), we and other groups have attempted to isolate such complexes in the past few years. Typical metal carbonyl complexes release CO when exposed to UV light, a fact that often deters their use in biological systems. From the very beginning, our effort therefore was directed toward identifying design principles that could lead to photoCORMs that release CO upon illumination with low-power (5-15 mW/cm(2)) visible and near-IR light. In our work, we have utilized Mn(I), Re(I), and Ru(II) centers (all d(6) ground state configuration) to ensure overall stability of the carbonyl complexes. We also hypothesized that transfer of electron density from the electron-rich metal centers to π* MOs of the ligand frame via strong metal-to-ligand charge transfer (MLCT) transitions in the visible/near-IR region would weaken metal-CO back-bonding and promote rapid CO photorelease. This expectation has been realized in a series of carbonyl complexes derived from a variety of designed ligands and smart choice of ligand/coligand combinations. Several principles have emerged from our systematic approach to the design of principal ligands and the choice of auxiliary ligands (in addition to the number of CO) in synthesizing these photoCORMs. In each case, density functional theory (DFT) and time-dependent DFT (TDDFT) study afforded insight into the dependence of the CO photorelease from a particular photoCORM on the wavelength of light. Results of these theoretical studies indicate that extended

  9. High Pressure Synthesis of Transition Metal Carbonyls.

    ERIC Educational Resources Information Center

    Hagen, A. P.; And Others

    1979-01-01

    Presents an experiment which uses readily available starting materials and inexpensive equipment for synthesis of transition metal carbonyls at 1000 atm and which is intended to give students experience in techniques used in research and industry. Safety precautions are emphasized. (Author/SA)

  10. Hydrogenation of coal liquid utilizing a metal carbonyl catalyst

    DOEpatents

    Feder, Harold M.; Rathke, Jerome W.

    1979-01-01

    Coal liquid having a dissolved transition metal, catalyst as a carbonyl complex such as Co.sub.2 (CO.sub.8) is hydrogenated with hydrogen gas or a hydrogen donor. A dissociating solvent contacts the coal liquid during hydrogenation to form an immiscible liquid mixture at a high carbon monoxide pressure. The dissociating solvent, e.g. ethylene glycol, is of moderate coordinating ability, while sufficiently polar to solvate the transition metal as a complex cation along with a transition metal, carbonyl anion in solution at a decreased carbon monoxide pressure. The carbon monoxide pressure is reduced and the liquids are separated to recover the hydrogenated coal liquid as product. The dissociating solvent with the catalyst in ionized form is recycled to the hydrogenation step at the elevated carbon monoxide pressure for reforming the catalyst complex within fresh coal liquid.

  11. Copper-incorporated mono- and di-TeRu5 metal carbonyl complexes: syntheses, structures, and an unusual skeletal arrangement.

    PubMed

    Shieh, Minghuey; Miu, Chia-Yeh; Hsing, Kai-Jieah; Jang, Li-Fing; Lin, Chien-Nan

    2015-04-14

    Two sandwich-type Cu3Cl- or Cu2{Te2Ru4(CO)10}-bridging di-TeRu5 clusters, [{TeRu5(CO)14}2Cu3Cl](2-) () and [{TeRu5(CO)14}2Cu2{Te2Ru4(CO)10}](4-) (), were obtained from the reaction of [TeRu5(CO)14](2-) with 1 equiv. of [Cu(MeCN)4][BF4] in CH2Cl2 or THF at 0 °C, respectively, depending on the solvents. The chloride-abstracted was structurally characterized to have two TeRu5 cores that were linked by a Cu3Cl moiety with two Cu-Cu bonds. If the reaction was carried out in a molar ratio of 1 : 2 at 0 or 30 °C in CH2Cl2, the structural isomers [TeRu5(μ-CO)2(CO)12(CuMeCN)2] () and [TeRu5(μ-CO)3(CO)11Cu2(MeCN)2] () were produced, respectively, as the major product. Cluster displayed a TeRu5 core with two adjacent Ru3 triangles each capped by a μ3-Cu(MeCN) fragment, while contained a TeRu5 core with one triangle Ru3 plane capped by a Cu2(MeCN)2 fragment with two Cu atoms covalently bonded. Upon heating, the isomerization of into proceeded to undergo an unusual skeletal arrangement of Cu(MeCN) and migration of CO, with the TeRu5 core remaining intact. An electrochemical study revealed that and each exhibited only one oxidation while cluster had two consecutive oxidations, suggesting significant electronic communication between the two TeRu5 metal cores in via the Cu3 moiety. This work describes the facile synthesis of a series of semiconducting Cux-bridging Te-Ru carbonyl clusters, in which the incorporation of the Cux fragments has significantly influenced their resulting structures, rearrangements, and electronic properties, which was further elucidated by DFT calculations.

  12. Catalytic production of metal carbonyls from metal oxides

    DOEpatents

    Sapienza, R.S.; Slegeir, W.A.; Foran, M.T.

    1984-01-06

    This invention relates to the formation of metal carbonyls from metal oxides and specially the formation of molybdenum carbonyl and iron carbonyl from their respective oxides. Copper is used here in admixed form or used in chemically combined form as copper molybdate. The copper/metal oxide combination or combined copper is utilized with a solvent, such as toluene and subjected to carbon monoxide pressure of 25 atmospheres or greater at about 150 to 260/sup 0/C. The reducing metal copper is employed in catalytic concentrations or combined concentrations as CuMoO/sub 4/ and both hydrogen and water present serve as promoters. It has been found that the yields by this process have been salutary and that additionally the catalytic metal may be reused in the process to good effect. 3 tables.

  13. Catalytic production of metal carbonyls from metal oxides

    DOEpatents

    Sapienza, Richard S.; Slegeir, William A.; Foran, Michael T.

    1984-01-01

    This invention relates to the formation of metal carbonyls from metal oxides and specially the formation of molybdenum carbonyl and iron carbonyl from their respective oxides. Copper is used here in admixed form or used in chemically combined form as copper molybdate. The copper/metal oxide combination or combined copper is utilized with a solvent, such as toluene and subjected to carbon monoxide pressure of 25 atmospheres or greater at about 150.degree.-260.degree. C. The reducing metal copper is employed in catalytic concentrations or combined concentrations as CuMoO.sub.4 and both hydrogen and water present serve as promoters. It has been found that the yields by this process have been salutary and that additionally the catalytic metal may be reused in the process to good effect.

  14. Vibrational spectra and structure of {open_quotes}staircase{close_quotes} carbonyl {pi}-complexes of transition metals 2. Rotational isomerism

    SciTech Connect

    Ezernitskaya, M.G.; Lokshin, B.V.; Orlova, T.Yu.; Setkina, V.N.; Shilnikov, V.I.; Cesaro, S.N.

    1995-05-01

    FTIR spectra have been studied for {open_quotes}staircase{close_quotes} cyclopentadienyl complexes containing two or three metal carbonyl fragments bound by the metal-carbon bond Cp(CO){sub 2}Fe-CpmMn(CO){sub 3} (1), Cp(CO){sub 2}Fe-CpmFe(CO){sub 2}CH{sub 2}Ph, Cp(CO){sub 2}Fe-Cpm(CO){sub 2}Fe-CpmMn(CO){sub 3}, Cp(CO){sub 2}Mo-Cpm(CO){sub 2}Fe-CpmMn(CO){sub 3}, Cp(CO){sub 3}W-Cpm(CO){sub 2}Fe-CpmMn(CO){sub 3}, Cp(CO){sub 2}Fe-Cpm(CO){sub 2}Fe-BmCr(CO){sub 3}, Cr(CO){sub 3}Bm-CpmFe(CO){sub 2}CH{sub 2}Ph, where Cp = {eta}{sup 5}-C{sub 5}H{sub 5}, Cpm = {eta}{sup 1}:{eta}{sup 5}-C{sub 5}H{sub 4}, Bm = {eta}{sup 1}:{eta}{sup 6}-C{sub 6}H{sub 5}. Temperature-dependent FTIR spectra were measured in n-pentane solutions over a wide temperature range and in the low-temperature solid matrices of argon and nitrogen. Rotamers, formed due to rotation about the metal-carbon {sigma}-bond, were found in solutions and matrices. A molecular mechanics calculation of 1 proved the possibility of such rotation.

  15. Vibrational spectra and structure of {open_quotes}staircase{close_quotes} carbonyl {pi}-complexes of transition metals 1. Electronic effects

    SciTech Connect

    Ezernitskaya, M.G.; Lokshin, B.V.; Orlova, T.Yu.; Setkina, V.N.; Cesaro, S.N.

    1995-05-01

    FTIR spectra have been studied for {open_quotes}staircase{close_quotes} cyclopentadienyl complexes comprising two or three metal carbonyl fragments bound by the metal-carbon bond Cp(CO){sub 2}Fe-CpmMn(CO){sub 3}, Cp(CO){sub 2}Fe-CpmFe(CO){sub 2}CH{sub 2}Ph, Cp(CO){sub 2}Fe-Cpm(CO){sub 2}Fe-CpmMn(CO){sub 3}, Cp(CO){sub 2}Mo-Cpm(CO){sub 2}Fe-CpmMn(CO){sub 3}, Cp(CO){sub 3}W-Cpm(CO){sub 2}Fe-CpmMn(CO){sub 3}, Cp(CO){sub 2}Fe-Cpm(CO){sub 2}Fe-BmCr(CO){sub 3}, Cr(CO){sub 3}Bm-CpmFe(CO){sub 2}CH{sub 2}Ph, where Cp = {eta}{sup 5}-C{sub 5}H{sub 5}, Cpm = {eta}{sup 1}: {eta}{sup 5}-C{sub 5}H{sub 4}, Bm = {eta}{sup 1}:{eta}{sup 6}-C{sub 6}H{sub 5}, as well as mononuclear model complexes Cp(CO){sub 2}Fe(CH){sub 2}Ph, CpMn(CO){sub 3}, and ({eta}{sup 6}-C{sub 6}H{sub 6})Cr(CO){sub 3}. The spectra were interpreted on the basis of the local symmetry of each metal carbonyl center. The positions of vCOs are determined by the mutual electronic effect of each center. CpmM(CO){sub n} groups are strong electron acceptors and cause an increase in vCOs of adjacent M(CO){sub n} groups. Cp(CO){sub n}M groups, being electron donors, cause a decrease in the frequencies of neighboring groups. In trinuclear complexes, the frequencies of the central Fe(CO){sub 2} group are not changed much due to the compensation of donor and acceptor influences of two neighboring substituents.

  16. Carbonyl mediated conductance through metal bound peptides: a computational study

    NASA Astrophysics Data System (ADS)

    Perrine, Trilisa M.; Dunietz, Barry D.

    2007-10-01

    Large increases in the conductance of peptides upon binding to metal ions have recently been reported experimentally. The mechanism of the conductance switching is examined computationally. It is suggested that oxidation of the metal ion occurs after binding to the peptide. This is caused by the bias potential placed across the metal-peptide complex. A combination of configurational changes, metal ion involvement and interactions between carbonyl group oxygen atoms and the gold leads are all shown to be necessary for the large improvement in the conductance seen experimentally. Differences in the molecular orbitals of the nickel and copper complexes are noted and serve to explain the variation of the improvement in conductance upon binding to either a nickel or copper ion.

  17. Metal carbonyl complexes with Schiff bases derived from 2-pyridinecarboxaldehyde: Syntheses, spectral, catalytic activity and antimicrobial activity studies

    NASA Astrophysics Data System (ADS)

    Ali, Omyma A. M.; El-Medani, Samir M.; Ahmed, Doaa A.; Nassar, Doaa A.

    2014-09-01

    Thermal reactions of [M(CO)6], M = Cr, Mo and W with the two Schiff bases: 2-[(pyridin-2-ylmethylidene)amino]-6-aminopyridine (L1) and 2-[(pyridin-2-ylmethylidene)amino]phenol (HL2) were investigated. Three complexes with molecular formulas [Cr(L1)3], 1, [MoO2(L1)2], 2 and [WO2(L1)2], 3 were isolated from the reactions with L1. The corresponding reactions with HL2 produced the complexes [Cr(HL2)2], 4, [Mo2(CO)4O2(HL2)2], 5 and [W(CO)4(HL2)], 6. All complexes were characterized by elemental analysis, infrared, mass and 1H NMR spectroscopy. The molar conductivities of the complexes in DMF indicated nonelectrolytic behavior. The prepared ligands and their complexes exhibited intraligand (π-π*) fluorescence and can potentially serve as photoactive materials. The catalytic activity of the complexes towards to hydrogen peroxide decomposition reaction was investigated. Both the ligands and their complexes have been screened for antibacterial activities.

  18. Liquid injection field desorption ionization mass spectrometry of cyclic metal carbonyl complexes with tetra-antimony ligands.

    PubMed

    Breunig, Hans J; Linden, H Bernhard; Moldovan, Ovidiu

    2013-01-01

    Reactions of (norbornadiene)Cr(CO)(4) or cis-(piperidine)(2)Mo(CO)(4) with R(2)Sb-SbR(2), and cyclo-(R'Sb)(n) (R' = Et, n-Pr; n = 4, 5) give the complexes cyclo-[M(CO)(4)(R(2)Sb-SbR'- SbR'-SbR(2))] (1: M = Cr, R = Me, R'= Et; 2: M = Mo, R = Et, R' = Et; 3: M = Mo, R = Et, R' = n-Pr). Not accessible to established characterization methods, the oily, extremely reactive unpurified mixture of 3 with scrambled ligands was characterized by mass spectrometry using liquid injection field desorption ionization (LIFDI).

  19. Transition-metal-catalyzed carbonylation reactions of olefins and alkynes: a personal account.

    PubMed

    Wu, Xiao-Feng; Fang, Xianjie; Wu, Lipeng; Jackstell, Ralf; Neumann, Helfried; Beller, Matthias

    2014-04-15

    carbonyls, carbon dioxide also offers interesting options. Industrial chemists seek easy to prepare catalysts and patent-free ligands/complexes. In addition, non-noble metal complexes will interest both academic and industrial researchers. The novel Lucite process for methyl methacrylate is an important example of an improved catalyst. This reaction makes use of a specific palladium/bisphosphine catalyst, which led to the successful implementation of the technology. More active and productive catalysts for related carbonylations of less reactive olefins would allow for other large scale applications of this methodology. From an academic point of view, researchers continue to look for selective reactions with more functionalized olefins. Finally, because of the volatility of simple metal carbonyl complexes, carbonylation reactions today remain a domain of homogeneous catalysis. The invention of more stable and recyclable heterogeneous catalysts or metal-free carbonylations (radical carbonylations) will be difficult, but could offer interesting challenges for young chemists.

  20. Liquid Injection Field Desorption Ionization Mass Spectrometry of Cyclic Metal Carbonyl Complexes with Tetra-Antimony Ligands

    NASA Astrophysics Data System (ADS)

    Breunig, Hans J.; Linden, H. Bernhard; Moldovan, Ovidiu

    2013-01-01

    Reactions of (norbornadiene)Cr(CO)4 or cis-(piperidine)2Mo(CO)4 with R2Sb-SbR2, and cyclo-(R'Sb)n (R' = Et, n-Pr; n = 4, 5) give the complexes cyclo-[M(CO)4(R2Sb-SbR'- SbR'-SbR2)] ( 1: M = Cr, R = Me, R'= Et; 2: M = Mo, R = Et, R' = Et; 3: M = Mo, R = Et, R' = n-Pr). Not accessible to established characterization methods, the oily, extremely reactive unpurified mixture of 3 with scrambled ligands was characterized by mass spectrometry using liquid injection field desorption ionization (LIFDI). [Figure not available: see fulltext.

  1. Synthesis of metal-carbonyl-dendrimer-antibody immunoconjugates: towards a new format for carbonyl metallo immunoassay.

    PubMed

    Fischer-Durand, Nathalie; Salmain, Michèle; Rudolf, Bogna; Vessières, Anne; Zakrzewski, Janusz; Jaouen, Gérard

    2004-04-02

    We report the preparation of metal-carbonyl-dendrimer-antibody conjugates. These metal-carbonyl-multilabeled antibodies are designed to be used in a new solid-phase-format carbonyl metallo immunoassay (CMIA). A fourth-generation polyamidoamine dendrimer was labeled with 10-25 (eta5-cyclopentadienyl)iron dicarbonyl (eta1-N-succinimidyl) entities. An antibody was chemically modified at its carbohydrate chains by a site-directed process used to preserve the antigen-antibody binding site. The antibody was then coupled with the dendrimer labeled with 10 metal carbonyl groups. An average of 1.4 labeled dendrimers were grafted per antibody molecule. These metal-carbonyl-dendrimer-antibody conjugates were used as new universal detection reagents that recognize their specific antigens. The antigens were spotted onto nitrocellulose membranes and detected by using the conjugates in combination with Fourier transform infrared spectroscopy. A detection level in the range 5-200 pmol per membrane was achieved. This approach opens the way to a new CMIA format.

  2. Gas-phase chemistry of technetium carbonyl complexes.

    PubMed

    Wang, Yang; Qin, Zhi; Fan, Fang-Li; Haba, Hiromitsu; Komori, Yukiko; Cao, Shi-Wei; Wu, Xiao-Lei; Tan, Cun-Min

    2015-05-28

    Gas-phase chemical behaviors of short-lived technetium carbonyl complexes were studied using a low temperature isothermal chromatograph (IC) coupled with a (252)Cf spontaneous fission (SF) source. Fission products recoiled from the (252)Cf SF source were thermalized in a mixed gas containing CO, and then technetium carbonyl complexes were formed from reactions between CO gas and various technetium isotopes. A gas-jet system was employed to transport the volatile carbonyl complexes from a recoil chamber to the IC. Short IC columns made of Fluorinated Ethylene Propylene (FEP) Teflon and quartz were used to obtain chemical information about the technetium carbonyl complexes. The results for the (104)Tc-(106)Tc carbonyl complexes were found to be strongly influenced by the precursors, and showed the chemical behaviors of (104)Mo-(106)Mo carbonyl complexes, respectively. However, (107)Tc and (108)Tc could represent the chemical information of the element technetium due to their high independent yields and the very short half-lives of their precursors (107)Mo and (108)Mo. An adsorption enthalpy of about ΔHads = -43 kJ mol(-1) was determined for the Tc carbonyl complexes on both the Teflon and quartz surfaces by fitting the breakthrough curves of the (107)Tc and (108)Tc carbonyl complexes with a Monte Carlo simulation program. Chemical yields of around 25% were measured for the Tc carbonyl complexes relative to the transport yields obtained with the gas-jet transport of KCl aerosol particles with Ar carrier gas. Furthermore, the influence of a small amount of O2 gas on the yields of the Mo and Tc carbonyl complexes was studied.

  3. Gas-phase chemistry of ruthenium and rhodium carbonyl complexes.

    PubMed

    Cao, Shiwei; Wang, Yang; Qin, Zhi; Fan, Fangli; Haba, Hiromitsu; Komori, Yukiko; Wu, Xiaolei; Tan, Cunmin; Zhang, Xin

    2016-01-07

    Short-lived ruthenium and rhodium isotopes were produced from a (252)Cf spontaneous fission (SF) source. Their volatile carbonyl complexes were formed in gas-phase reactions in situ with the carbon-monoxide containing gas. A gas-jet system was employed to transport the volatile carbonyls from the recoil chamber to the chemical separation apparatus. The gas-phase chemical behaviors of these carbonyl complexes were studied using an online low temperature isothermal chromatography (IC) technique. Long IC columns made up of FEP Teflon were used to obtain the chemical information of the high-volatile Ru and Rh carbonyls. By excluding the influence of precursor effects, short-lived isotopes of (109-110)Ru and (111-112)Rh were used to represent the chemical behaviours of Ru and Rh carbonyls. Relative chemical yields of about 75% and 20% were measured for Ru(CO)5 and Rh(CO)4, respectively, relative to the yields of KCl aerosols transported in Ar gas. The adsorption enthalpies of ruthenium and rhodium carbonyl complexes on a Teflon surface were determined to be around ΔHads = -33(+1)(-2) kJ mol(-1) and -36(+2)(-1) kJ mol(-1), respectively, by fitting the breakthrough curves of the corresponding carbonyl complexes with a Monte Carlo simulation program. Different from Mo and Tc carbonyls, a small amount of oxygen gas was found to be not effective for the chemical yields of ruthenium and rhodium carbonyl complexes. The general chemical behaviors of short-lived carbonyl complexes of group VI-IX elements were discussed, which can be used in the future study on the gas-phase chemistry of superheavy elements - Bh, Hs, and Mt carbonyls.

  4. Half-Sandwich Metal Carbonyl Complexes as Precursors to Functional Materials: From a Near-Infrared-Absorbing Dye to a Single-Molecule Magnet.

    PubMed

    Wang, Wenqing; Li, Jing; Yin, Lei; Zhao, Yue; Ouyang, Zhongwen; Wang, Xinping; Wang, Zhenxing; Song, You; Power, Philip P

    2017-08-30

    Chemical oxidations of piano-stool chromium/cobalt carbonyl complexes Cr(CO)3(η(6),η(5)-C6H5C5H4)Co(CO)2 (1) and Cr(CO)3(η(6),η(6)-C6H5C6H5) Cr(CO)3 (2) were investigated. Upon one-electron oxidation, 1 was transformed to a heterometalloradical species, 1(•+). However, either one- or two-electron oxidation of 2 afforded a decomposition product, 3. Dipping 3 into pentane led to the formation of 4 via a crystal-to-crystyal transformation with the removal of solvent molecules. Complexes 1(•+) and 4 were fully characterized by various spectroscopic techniques and single-crystal X-ray analysis. Cation 1(•+) features a weak Cr-Co bond with a Wiberg bond order of 0.278. A near-infrared absorption band around 1031 nm was observed for 1(•+), which is far red-shifted in comparison to previously reported dinuclear metalloradical species. Complex 4 contains a chromium(II) with a distorted pyramidal geometry and displays single-molecule magnetic properties.

  5. Metal-Diazo Radicals of α-Carbonyl Diazomethanes

    PubMed Central

    Li, Feifei; Xiao, Longqiang; Liu, Lijian

    2016-01-01

    Metal-diazo radicals of α-carbonyl diazomethanes are new members of the radical family and are precursors to metal-carbene radicals. Herein, using electron paramagnetic resonance spectroscopy with spin-trapping, we detect diazo radicals of α-carbonyl diazomethanes, induced by [RhICl(cod)]2, [CoII(por)] and PdCl2, at room temperature. The unique quintet signal of the Rh-diazo radical was observed in measurements of α-carbonyl diazomethane adducts of [RhICl(cod)]2 in the presence of 5,5-dimethyl-pyrroline-1-N-oxide (DMPO). DFT calculations indicated that 97.2% of spin density is localized on the diazo moiety. Co- and Pd-diazo radicals are EPR silent but were captured by DMPO to form spin adducts of DMPO-N∙ (triplet-of-sextets signal). The spin-trapping also provides a powerful tool for detection of metal-carbene radicals, as evidenced by the DMPO-trapped carbene radicals (DMPO-C∙, sextet signal) and 2-methyl-2-nitrosopropane-carbene adducts (MNP-C∙, doublet-of-triplets signal). The transformation of α-carbonyl diazomethanes to metal-carbene radicals was confirmed to be a two-step process via metal-diazo radicals. PMID:26960916

  6. Metal-Diazo Radicals of α-Carbonyl Diazomethanes

    NASA Astrophysics Data System (ADS)

    Li, Feifei; Xiao, Longqiang; Liu, Lijian

    2016-03-01

    Metal-diazo radicals of α-carbonyl diazomethanes are new members of the radical family and are precursors to metal-carbene radicals. Herein, using electron paramagnetic resonance spectroscopy with spin-trapping, we detect diazo radicals of α-carbonyl diazomethanes, induced by [RhICl(cod)]2, [CoII(por)] and PdCl2, at room temperature. The unique quintet signal of the Rh-diazo radical was observed in measurements of α-carbonyl diazomethane adducts of [RhICl(cod)]2 in the presence of 5,5-dimethyl-pyrroline-1-N-oxide (DMPO). DFT calculations indicated that 97.2% of spin density is localized on the diazo moiety. Co- and Pd-diazo radicals are EPR silent but were captured by DMPO to form spin adducts of DMPO-N• (triplet-of-sextets signal). The spin-trapping also provides a powerful tool for detection of metal-carbene radicals, as evidenced by the DMPO-trapped carbene radicals (DMPO-C•, sextet signal) and 2-methyl-2-nitrosopropane-carbene adducts (MNP-C•, doublet-of-triplets signal). The transformation of α-carbonyl diazomethanes to metal-carbene radicals was confirmed to be a two-step process via metal-diazo radicals.

  7. Metal-atom fluorescence from the quenching of metastable rare gases by metal carbonyls

    SciTech Connect

    Hollingsworth, W.E.

    1982-11-01

    A flowing afterglow apparatus was used to study the metal fluorescence resulting from the quenching of metastable rare-gas states by metal carbonyls. The data from the quenching or argon, neon, and helium by iron and nickel carbonyl agreed well with a restricted degree of freedom model indicating a concerted bond-breaking dissociation.

  8. Hexaruthenium carbonyl cluster complexes with basal edge-bridged square pyramidal metallic skeleton: efficient synthesis of 2-imidopyridine derivatives and determination of their reactive sites in carbonyl substitution reactions.

    PubMed

    Cabeza, Javier A; del Río, Ignacio; García-Alvarez, Pablo; Miguel, Daniel; Riera, Víctor

    2004-08-23

    The reactions of [Ru(3)(CO)(12)] with half equivalent of 2-amino-6-methylpyridine (H(2)ampy) or 2-aminopyridine (H(2)apy) in refluxing xylene give the hexanuclear products [Ru(6)(mu(3)-H)(2)(mu(5)-eta(2)-L)(mu-CO)(2)(CO)(14)] (L = ampy, 1; apy, 2). These reactions represent the first high-yield syntheses of hexanuclear complexes with a basal edge-bridged square pyramidal metallic skeleton. Five metal atoms of these complexes are bridged by the N-donor ligand in such a way that the edge-bridging metal atom is attached to the pyridine nitrogen, while the basal atoms of the square pyramid are capped by an imido fragment that arises from the activation of both N-H bonds of the NH(2) group. The reactive sites of these complexes in CO substitution reactions have been determined by studying the reactivity of 1 with triphenylphosphine. Two kinetically controlled monosubstitutions take place on the edge-bridging metal atom in positions cis to the pyridine nitrogen, leading to a mixture of two isomers of formula [Ru(6)(mu(3)-H)(2)(mu(5)-eta(2)-ampy)(mu-CO)(2)(CO)(13)(PPh(3))] (3 and 4). On heating at 80 degrees C, these monosubstituted isomers are transformed, via a dissociative pathway, into the product of thermodynamic control (5), which has the PPh(3) ligand on the apical Ru atom. The di- and trisubstituted derivatives [Ru(6)(mu(3)-H)(2)(mu(5)-eta(2)-ampy)(mu-CO)(2)(CO)(12)(PPh(3))(2)] (6) and [Ru(6)(mu(3)-H)(2)(mu(5)-eta(2)-ampy)(mu-CO)(2)(CO)(11)(PPh(3))(3)] (7) are stepwise formed from 3-5 and PPh(3). Compound 6 has the PPh(3) ligands on the edge-bridging and apical Ru atoms, and compound 7 has an additional PPh(3) ligand on an unbridged basal Ru atom. The compound [Ru(6)(mu(3)-H)(2)(mu(5)-eta(2)-ampy)(mu-CO)(2)(CO)(12)(mu-dppm)] (8), in which a basal and the apical Ru atoms are spanned by the dppm ligand, has been isolated from the reaction of 1 with bis(diphenylphosphino)methane.

  9. Opening of Carborane Cages by Metal Cluster Complexes: The Reaction of a Thiolate-Substituted Carborane with Triosmium Carbonyl Cluster Complexes.

    PubMed

    Adams, Richard D; Kiprotich, Joseph; Peryshkov, Dmitry V; Wong, Yuen Onn

    2016-08-15

    The reaction of Os3(CO)10(NCMe)2 with closo-o-(1-SCH3)C2B10H11 has yielded the complex Os3(CO)9[μ3-η(3)-C2B10H9(SCH3)](μ-H)2, 1, by the loss of the two NCMe ligands and one CO ligand from the Os3 cluster and the coordination of the sulfur atom and the activation of two B-H bonds with transfer of the hydrogen atoms to the cluster. Reaction of 1 with a second equivalent of Os3(CO)10(NCMe)2 yielded the complex Os3(CO)9(μ-H)[(μ3-η(3)-1,4,5-μ3-η(3)-6,10,11-C2B10H8S(CH3)]Os3(CO)9(μ-H)2, 2, that contains two triosmium triangles attached to the same carborane cage. The carborane cage was opened by cleavage of two B-C bonds and one B-B bond. The B-H group that was pulled out of the cage became a triply bridging group on one of the Os3 triangles but remains bonded to the cage by two B-B bonds. When heated to 150 °C, 2 was transformed into the complex Os3(CO)9(μ-H)[(μ3-η(3)-μ3-η(3)-C2B10H7S(CH3)]Os3(CO)9(μ-H), 3, by the loss of two hydrogen atoms and a rearrangement that led to further opening of the carborane cage. Reaction of 1 with a second equivalent of closo-o-(1-SCH3)C2B10H11 has yielded the complex Os3(CO)6)(μ3-η(3)-C2B10H9-R-SCH3) (μ3-η(3)-C2B10H10-S-SCH3)(μ-H)3, 4a, containing two carborane cages coordinated to one Os3 cluster. Compound 4a was isomerized to the compound Os3(CO)6(μ3-η(3)-C2B10H9-R-SCH3)(μ3-η(3)-C2B10H10-R-SCH3)(μ-H)3, 4b, by an inversion of stereochemistry at one of the sulfur atoms by heating to 174 °C.

  10. The N-heterocyclic carbene chemistry of transition-metal carbonyl clusters.

    PubMed

    Cabeza, Javier A; García-Álvarez, Pablo

    2011-11-01

    In the last decade, chemists have dedicated many efforts to investigate the coordination chemistry of N-heterocyclic carbenes (NHCs). Although most of that research activity has been devoted to mononuclear complexes, transition-metal carbonyl clusters have not escaped from these investigations. This critical review, which is focussed on the reactivity of NHCs (or their precursors) with transition-metal carbonyl clusters (mostly are of ruthenium and osmium) and on the transformations underwent by the NHC-containing species initially formed in those reactions, shows that the polynuclear character of these metallic compounds or, more precisely, the close proximity of one or more metal atoms to that which is or can be attached to the NHC ligand, is responsible for reactivity patterns that have no parallel in the NHC chemistry of mononuclear complexes (74 references).

  11. Iron-Sulfur-Carbonyl and -Nitrosyl Complexes: A Laboratory Experiment.

    ERIC Educational Resources Information Center

    Glidewell, Christopher; And Others

    1985-01-01

    Background information, materials needed, procedures used, and typical results obtained, are provided for an experiment on iron-sulfur-carbonyl and -nitrosyl complexes. The experiment involved (1) use of inert atmospheric techniques and thin-layer and flexible-column chromatography and (2) interpretation of infrared, hydrogen and carbon-13 nuclear…

  12. Iron-Sulfur-Carbonyl and -Nitrosyl Complexes: A Laboratory Experiment.

    ERIC Educational Resources Information Center

    Glidewell, Christopher; And Others

    1985-01-01

    Background information, materials needed, procedures used, and typical results obtained, are provided for an experiment on iron-sulfur-carbonyl and -nitrosyl complexes. The experiment involved (1) use of inert atmospheric techniques and thin-layer and flexible-column chromatography and (2) interpretation of infrared, hydrogen and carbon-13 nuclear…

  13. Infrared spectra and density functional theory calculations of the tantalum and niobium carbonyl dinitrogen complexes.

    PubMed

    Lu, Zhang-Hui; Jiang, Ling; Xu, Qiang

    2009-07-21

    Laser-ablated tantalum and niobium atoms react with CO and N(2) mixtures in excess neon to produce carbonyl metal dinitrogen complexes, NNMCO (M = Ta, Nb), (NN)(2)TaCO, and NNTa(CO)(2), as well as metal carbonyls and dinitrogen complexes. These carbonylmetal dinitrogen complexes are characterized using infrared spectroscopy on the basis of the results of the isotopic substitution and mixed isotopic splitting patterns. Density functional theory calculations have been performed on these novel species. The good agreement between the experimental and calculated vibrational frequencies, relative absorption intensities, and isotopic shifts supports the identification of these species from the matrix infrared spectra. Natural bond orbital analysis and plausible reaction mechanisms for the formation of the products are discussed.

  14. Metal Carbonyl-Hydrosilane Reactions and Hydrosilation Catalysis

    SciTech Connect

    Cutler, A. R.

    2001-04-14

    Manganese carbonyl complexes serve as hydrosilation precatalysts for selectively transforming a carbonyl group into a siloxy methylene or a fully reduced methylene group. Substrates of interest include (1) aldehydes, ketones, carboxylic acids, silyl esters, and esters, and (2) their organometallic acyl counterparts. Three relevant catalytic reactions are shown. Two types of manganese precatalysts have been reported: (a) alkyl and acyl complexes (L)(C0){sub 4}MnR [L = CO, PPh{sub 3}; R = COCH{sub 3}, COPh, CH{sub 3}] and (b) halides (CO){sub 5}MnX and [(CO){sub 4}MnX]{sub 2} (X = Br, I). The former promote hydrosilation and deoxygenation catalysis; the latter promote dehydrogenative silation of alcohols and carboxylic acids as well as hydrosilation and deoxygenation of some metallocarboxylic acid derivatives. In every case studied, these Mn precatalysts are far more reactive or selective than traditional Rh(I) precatalysts.

  15. Nuclear chemistry. Synthesis and detection of a seaborgium carbonyl complex.

    PubMed

    Even, J; Yakushev, A; Düllmann, Ch E; Haba, H; Asai, M; Sato, T K; Brand, H; Di Nitto, A; Eichler, R; Fan, F L; Hartmann, W; Huang, M; Jäger, E; Kaji, D; Kanaya, J; Kaneya, Y; Khuyagbaatar, J; Kindler, B; Kratz, J V; Krier, J; Kudou, Y; Kurz, N; Lommel, B; Miyashita, S; Morimoto, K; Morita, K; Murakami, M; Nagame, Y; Nitsche, H; Ooe, K; Qin, Z; Schädel, M; Steiner, J; Sumita, T; Takeyama, M; Tanaka, K; Toyoshima, A; Tsukada, K; Türler, A; Usoltsev, I; Wakabayashi, Y; Wang, Y; Wiehl, N; Yamaki, S

    2014-09-19

    Experimental investigations of transactinoide elements provide benchmark results for chemical theory and probe the predictive power of trends in the periodic table. So far, in gas-phase chemical reactions, simple inorganic compounds with the transactinoide in its highest oxidation state have been synthesized. Single-atom production rates, short half-lives, and harsh experimental conditions limited the number of experimentally accessible compounds. We applied a gas-phase carbonylation technique previously tested on short-lived molybdenum (Mo) and tungsten (W) isotopes to the preparation of a carbonyl complex of seaborgium, the 106th element. The volatile seaborgium complex showed the same volatility and reactivity with a silicon dioxide surface as those of the hexacarbonyl complexes of the lighter homologs Mo and W. Comparison of the product's adsorption enthalpy with theoretical predictions and data for the lighter congeners supported a Sg(CO)6 formulation.

  16. Benchmark calculations of metal carbonyl cations: relativistic vs. electron correlation effects.

    PubMed

    Matito, Eduard; Salvador, Pedro; Styszyński, Jacek

    2013-12-14

    In this paper we present benchmark results for isoelectronic metal carbonyl complexes of the groups 11 and 12 of the periodic table. The focus is on the geometry, vibrational frequencies, bond dissociation energy and chemical bonding. The description of these complexes requires a good balance between electron correlation and relativistic effects. Our results demonstrate that the combination of the effective core potential and the MP2 method gives quantitative results for the first- and the second-row transition metal complexes and only qualitative agreement for the third-row complexes. In order to obtain quantitative results for the whole series the use of four-component or X2C methods is mandatory. The fourth-row transition metal carbonyl complexes from groups 11 and 12 have been studied for the first time. The metal-carbon bond strength pattern along the group is shown to be highly dependent on the correct description of the relativistic effects. Finally, the relativistic effects on the bonding are studied by means of electron density difference maps, the analysis of the bond critical points of the electron density and the mechanism for σ-donation and π-backdonation. Our analysis indicates that the fourth-row complexes exhibit a strong covalent character induced by relativistic effects.

  17. Transition-Metal-Catalyzed Carbonylation of Methyl Acetate.

    ERIC Educational Resources Information Center

    Polichnowski, S. W.

    1986-01-01

    Presents a study of the rhodium-catalyzed, ioding-promoted carbonylation of methyl acetate. This study provides an interesting contrast between the carbonylation of methyl acetate and the carbonylation of methanol when similar rhodium/iodine catalyst systems are used. (JN)

  18. Transition-Metal-Catalyzed Carbonylation of Methyl Acetate.

    ERIC Educational Resources Information Center

    Polichnowski, S. W.

    1986-01-01

    Presents a study of the rhodium-catalyzed, ioding-promoted carbonylation of methyl acetate. This study provides an interesting contrast between the carbonylation of methyl acetate and the carbonylation of methanol when similar rhodium/iodine catalyst systems are used. (JN)

  19. Dimetallocene Carbonyls of the Third-Row Transition Metals: The Quest for High-Order Metal-Metal Multiple Bonds

    NASA Astrophysics Data System (ADS)

    Xu, Bing; Li, Qian-Shu; Xie, Yaoming; King, R. Bruce; Schaefer, Henry F.

    2009-07-01

    Theoretical studies of the third-row transition-metal derivatives Cp2M2(CO) (Cp = η5-C5H5; M = Os, Re, W, Ta) indicate that the lowest-energy structures have lower spin states and similar or higher metal-metal bond multiplicities than the corresponding first-row transtion-metal derivatives. Therefore, Cp2Os2(CO) is predicted to be a singlet with an Os-Os formal quadruple bond, whereas Cp2Fe2(CO) is a triplet. Similarly, Cp2Re2(CO) is predicted to be a singlet with a very short rhenium-rhenium distance, which is consistent with the formal quintuple bond required to give both rhenium-rhenium atoms the favored 18-electron configuration. This contrasts with the manganese analogue Cp2Mn2(CO) for which the lowest-energy structure is a septet with a formal Mn-Mn single bond. The tungsten derivative Cp2W2(CO) is predicted to be triplet with a four-electron donor bridging carbonyl group. This contrasts with Cp2Cr2(CO) predicted to be a septet (S = 3) with a two-electron donor carbonyl group. For Cp2Ta2(CO), the lowest-energy structure is predicted to be a triplet with a formal Ta≡Ta triple bond and a four-electron donor carbonyl group. However, Cp2V2(CO) is predicted to be a quintet with a formal V═V double bond. In addition to these Cp2M2(CO) structures with one Cp ring bonded to each metal atom, higher-energy Cp2M-MCO structures are found with both Cp rings bonded to the same metal atom. The lowest-energy Cp2M-MCO structures are triplets (M = Os, W) or quintets (M = Re) with agostic hydrogen atoms for M = Os and Re. In these structures, the spin density is concentrated on the metal atom of the MCO group. These results suggest that lower spin states clearly become more viable for highly unsaturated metal complexes upon descending the periodic table.

  20. Structure, photophysics, electrochemistry, DFT calculation, and in-vitro antioxidant activity of coumarin Schiff base complexes of Group 6 metal carbonyls.

    PubMed

    Datta, Papia; Mukhopadhyay, Ambika Prasad; Manna, Prasenjit; Tiekink, Edward R T; Sil, Parames Chandra; Sinha, Chittaranjan

    2011-04-01

    N-[(2-Pyridyl)methyliden]-6-coumarin (L) is synthesized by the condensation of 6-aminocoumarin and pyridine-2-carboxaldehyde. Group-6 tetracarbonyl complexes, [M(CO)(4)(L)] (M=Cr, Mo, and W) are synthesized and characterized by mass spectrometry and NMR, FT-IR and UV-visible spectroscopy. X-ray crystal structure of [Cr(CO)(4)(L)] shows N(pyridine), N(imine) chelation to chromium(0). A supramolecular chain is formed by C-H⋯O and π⋯π interactions. The ligand and the complexes are fluorescent. Cyclic voltammetry of the complexes exhibit quasireversible M(I)/M(0) redox couple. The complexes exhibit potential antioxidant property both in cell free and in-vitro studies and highest activity is observed to [W(CO)(4)(L)]. Density functional theory (DFT) computation has been performed to correlate with the electronic configuration, composition of wave functions with the UV-visible spectra and redox properties.

  1. Reactions of isocyanide-substituted dimanganese carbonyl complexes with alkynes. Alkyne-isocyanide coupling and the synthesis of metalated n-substituted pyridines

    SciTech Connect

    Adams, R.D.; Huang, M. )

    1995-01-01

    When activated by Me[sub 3]NO in the presence of MeCN, the compounds Mn[sub 2](CO)[sub 9](CNR) (la,b; R = Me, Ph) react with MeO[sub 2]O[sub 2]CC[triple bond]CCO[sub 2]Me to yield the new compounds Mn[sub 2](CO)[sub 8][[mu]-(MeO[sub 2]C)C=C(CO[sub 2]Me)C=NR] (2a,b; R = Me, Ph) in yields of 40% and 32%, respectively. Minor products, Mn[sub 2](CO)[sub 7](CNR)[[mu]-(MeO[sub 2]C)C=C(CO[sub 2]Me)-C=O] (3a,b; R = Me, Ph) were also formed. Compound 2a was characterized crystallographically. The structure shows that the isocyanide ligand was coupled to the alkyne, and the nitrogen atom is coordinated to one of the manganese atoms to form a five-membered cyclo-mangana enimine ring. One of the carboxylate groups is coordinated to the other manganese atom. The compounds (4a), (4b), and (4c) were prepared in yields of 27%, 32%, and 31%, respectively, by treatment of 2a,b with C[sub 2]H[sub 2], and of 2a with HC[sub 2](CO[sub 2]Me) in the presence of UV irradiation. Compound 4a was characterized crystallographically. This compound contains a metalated N-methylpyridine ring formed by a 1,4-cycloaddition of the alkyne to the enimine grouping in compound 2a. One of the metal atoms was shifted to a n-bonding coordination involving four of the carbon atoms of the pyridine ring. 14 refs., 2 figs., 7 tabs.

  2. Preparation of dinitrogen, hydrido, and carbonyl complexes of molybdenum and tungsten from higher halides

    SciTech Connect

    Borisov, A.P.; Makhaev, V.D.; Semenenko, K.N.

    1988-01-20

    The yields, physicochemical properties, and analyses of phosphine complexes of molybdenum and tungsten are shown. The reduction of molydenum pentachloride or tungsten hexachloride with metallic magnesium in THF in the presence of a tertiary organic phosphines in an atmosphere of nitrogen, hydrogen, or carbon monoxide provided a convenient method for the preparation of dinitrogen M(N/sub 2/)/sub 2/L/sub 4/, hydride MH/sub 4/L/sub 4/, or carbonyl M(CO)/sub 6/minus/x/L/sub x/ complexes respectively of molybdenum or tungsten (M = Mo, W; L - tertiary organic phosphine).

  3. CO-releasing Metal Carbonyl Compounds as Antimicrobial Agents in the Post-antibiotic Era*

    PubMed Central

    Wareham, Lauren K.; Poole, Robert K.; Tinajero-Trejo, Mariana

    2015-01-01

    The possibility of a “post-antibiotic era” in the 21st century, in which common infections may kill, has prompted research into radically new antimicrobials. CO-releasing molecules (CORMs), mostly metal carbonyl compounds, originally developed for therapeutic CO delivery in animals, are potent antimicrobial agents. Certain CORMs inhibit growth and respiration, reduce viability, and release CO to intracellular hemes, as predicted, but their actions are more complex, as revealed by transcriptomic datasets and modeling. Progress is hindered by difficulties in detecting CO release intracellularly, limited understanding of the biological chemistry of CO reactions with non-heme targets, and the cytotoxicity of some CORMs to mammalian cells. PMID:26055702

  4. Formation of vesicles with an organometallic amphiphile bilayer by supramolecular arrangement of metal carbonyl metallosurfactants.

    PubMed

    Parera, Elisabet; Comelles, Francesc; Barnadas, Ramon; Suades, Joan

    2011-04-21

    Metallo-vesicles are formed in water medium as a result of the supramolecular arrangement of molybdenum carbonyl metallosurfactants. These new kind of surfactants contain a hydrophobic metal carbonyl fragment and are easily prepared from surfactant phosphine ligands. © The Royal Society of Chemistry 2011

  5. Controlled Hydrosilylation of Carbonyls and Imines Catalyzed by a Cationic Alkyl Complex

    SciTech Connect

    Koller, Jurgen; Bergman, Robert G.

    2012-04-09

    The synthesis, characterization, and unprecedented catalytic activity of cationic aluminum alkyl complexes toward hydrosilylation are described. X-ray crystallographic analysis of Tp*AlMe₂ (1) and [Tp*AlMe][I₃] (3) revealed the preference of Al for a tetrahedral coordination environment and the versatility of the Tp* ligand in stabilizing Al in bi- and tridentate coordination modes. [Tp*AlMe][MeB(C₆F₅)₃] (2) is highly active toward the hydrosilylation of a wide variety of carbonyls and imines, thus providing an inexpensive and versatile alternative to late transition metal catalysts.

  6. Effect of hydrogen atoms on the structures of trinuclear metal carbonyl clusters: trinuclear manganese carbonyl hydrides.

    PubMed

    Liu, Xian-mei; Wang, Chao-yang; Li, Qian-shu; Xie, Yaoming; King, R Bruce; Schaefer, Henry F

    2009-05-18

    The structures of the trinuclear manganese carbonyl hydrides H(3)Mn(3)(CO)(n) (n = 12, 11, 10, 9) have been investigated by density functional theory (DFT). Optimization of H(3)Mn(3)(CO)(12) gives the experimentally known structure in which all carbonyl groups are terminal and each edge of a central Mn(3) equilateral triangle is bridged by a single hydrogen atom. This structure establishes the canonical distance 3.11 A for the Mn-Mn single bond satisfying the 18-electron rule. The central triangular (mu-H)(3)Mn(3) unit is retained in the lowest energy structure of H(3)Mn(3)(CO)(11), which may thus be derived from the H(3)Mn(3)(CO)(12) structure by removal of a carbonyl group with concurrent conversion of one of the remaining carbonyl groups into a semibridging carbonyl group to fill the resulting hole. The potential energy surface of H(3)Mn(3)(CO)(10) is relatively complicated with six singlet and five triplet structures. One of the lower energy H(3)Mn(3)(CO)(10) structures has one of the hydrogen atoms bridging the entire Mn(3) triangle and the other two hydrogen atoms bridging Mn-Mn edges. This H(3)Mn(3)(CO)(10) structure achieves the favored 18-electron configuration with a very short MnMn triple bond of 2.36 A. The other low energy H(3)Mn(3)(CO)(10) structure retains the (mu-H)(3)Mn(3) core of H(3)Mn(3)(CO)(12) but has a unique six-electron donor eta(2)-mu(3) carbonyl group bridging the entire Mn(3) triangle similar to the unique carbonyl group in the known compound Cp(3)Nb(3)(CO)(6)(eta(2)-mu(3)-CO). For H(3)Mn(3)(CO)(9) a structure with a central (mu(3)-H)(2)Mn(3) trigonal bipyramid lies >20 kcal/mol below any of the other structures. Triplet structures were found for the unsaturated H(3)Mn(3)(CO)(n) (n = 11, 10, 9) systems but at significantly higher energies than the lowest lying singlet structures.

  7. Nickel and iron pincer complexes as catalysts for the reduction of carbonyl compounds.

    PubMed

    Chakraborty, Sumit; Bhattacharya, Papri; Dai, Huiguang; Guan, Hairong

    2015-07-21

    The reductions of aldehydes, ketones, and esters to alcohols are important processes for the synthesis of chemicals that are vital to our daily life, and the reduction of CO2 to methanol is expected to provide key technology for carbon management and energy storage in our future. Catalysts that affect the reduction of carbonyl compounds often contain ruthenium, osmium, or other precious metals. The high and fluctuating price, and the limited availability of these metals, calls for efforts to develop catalysts based on more abundant and less expensive first-row transition metals, such as nickel and iron. The challenge, however, is to identify ligand systems that can increase the thermal stability of the catalysts, enhance their reactivity, and bypass the one-electron pathways that are commonly observed for first-row transition metal complexes. Although many other strategies exist, this Account describes how we have utilized pincer ligands along with other ancillary ligands to accomplish these goals. The bis(phosphinite)-based pincer ligands (also known as POCOP-pincer ligands) create well-defined nickel hydride complexes as efficient catalysts for the hydrosilylation of aldehydes and ketones and the hydroboration of CO2 to methanol derivatives. The hydride ligands in these complexes are substantially nucleophilic, largely due to the enhancement by the strongly trans-influencing aryl groups. Under the same principle, the pincer-ligated nickel cyanomethyl complexes exhibit remarkably high activity (turnover numbers up to 82,000) for catalytically activating acetonitrile and the addition of H-CH2CN across the C═O bonds of aldehydes without requiring a base additive. Cyclometalation of bis(phosphinite)-based pincer ligands with low-valent iron species "Fe(PR3)4" results in diamagnetic Fe(II) hydride complexes, which are active catalysts for the hydrosilylation of aldehydes and ketones. Mechanistic investigation suggests that the hydride ligand is not delivered to the

  8. High-resolution X-ray absorption spectroscopy of iron carbonyl complexes.

    PubMed

    Atkins, Andrew J; Bauer, Matthias; Jacob, Christoph R

    2015-06-07

    We apply high-energy-resolution fluorescence-detected (HERFD) X-ray absorption near-edge spectroscopy (XANES) to study iron carbonyl complexes. Mono-, bi-, and tri-nuclear carbonyl complexes and pure carbonyl complexes as well as carbonyl complexes containing hydrocarbon ligands are considered. The HERFD-XANES spectra reveal multiple pre-edge peaks with individual signatures for each complex, which could not be detected previously with conventional XANES spectroscopy. These peaks are assigned and analysed with the help of TD-DFT calculations. We demonstrate that the pre-edge peaks can be used to distinguish the different types of iron-iron interactions in carbonyl complexes. This opens up new possibilities for applying HERFD-XANES spectroscopy to probe the electronic structure of iron catalysts.

  9. Reactivity of Ir(III) carbonyl complexes with water: alternative by-product formation pathways in catalytic methanol carbonylation.

    PubMed

    Elliott, Paul I P; Haak, Susanne; Meijer, Anthony J H M; Sunley, Glenn J; Haynes, Anthony

    2013-12-21

    The reactions of water with a number of iridium(III) complexes relevant to the mechanism for catalytic methanol carbonylation are reported. The iridium acetyl, [Ir(CO)2I3(COMe)](-), reacts with water under mild conditions to release CO2 and CH4, rather than the expected acetic acid. Isotopic labeling and kinetic experiments are consistent with a mechanism involving nucleophilic attack by water on a terminal CO ligand of [Ir(CO)2I3(COMe)](-) to give an (undetected) hydroxycarbonyl species. Subsequent decarboxylation and elimination of methane gives [Ir(CO)2I2](-). Similar reactions with water are observed for [Ir(CO)2I3Me](-), [Ir(CO)2(NCMe)I2(COMe)] and [Ir(CO)3I2Me] with the neutral complexes exhibiting markedly higher rates. The results demonstrate that CO2 formation during methanol carbonylation is not restricted to the conventional water gas shift mechanism mediated by [Ir(CO)2I4](-) or [Ir(CO)3I3], but can arise directly from key organo-iridium(III) intermediates in the carbonylation cycle. An alternative pathway for methane formation not involving the intermediacy of H2 is also suggested. A mechanism is proposed for the conversion MeOH + CO → CO2 + CH4, which may account for the similar rates of formation of the two gaseous by-products during iridium-catalysed methanol carbonylation.

  10. The metal-carbonyl···π(aryl) interaction as a supramolecular synthon for the stabilisation of transition metal carbonyl crystal structures.

    PubMed

    Zukerman-Schpector, Julio; Haiduc, Ionel; Tiekink, Edward R T

    2011-12-21

    M-carbonyl(lone pair)···π(aryl) interactions provide stability to their transition metal crystal structures. This supramolecular synthon usually leads to zero- or one-dimensional aggregation patterns; a rare example of a three-dimensional architecture based on the M-CO(lone pair)···π(aryl) synthon has also been revealed.

  11. Is the C dbnd O frequency shift a reliable indicator of coumarin binding to metal ions through the carbonyl oxygen?

    NASA Astrophysics Data System (ADS)

    Georgieva, Ivelina; Trendafilova, Natasha; Creaven, Bernadette S.; Walsh, Maureen; Noble, Andy; McCann, Malachy

    2009-11-01

    The coumarin ligand, 4-hydroxy-3-nitro- 2H-chromen-2-one ( Hhnc) and its Cu(II) and Ag(I) complexes were studied by DFT calculations at B3LYP/B1 and PW91/B1 levels. MEP of the deprotonated ligand, hnc-, and energy calculations of model metal complexes predicted the ligand binding to the metal ion through the hydroxyl and the nitro oxygens in agreement with experiment. Based on precisely selected Cu/Ag model complexes with hnc-, a relation between the vibrational behaviour of the ligand donor groups and the ligand binding modes in the complexes was deduced. The observed carbonyl ν(C dbnd O) downshift (50-90 cm -1) is attributed to intermolecular H-bonding formed between the C dbnd O group and lattice water molecules or due to the C dbnd O binding to the metal ion in case of bridging coumarin ligand (in Aghnc). Much larger ν(C dbnd O) downshift (˜220-240 cm -1) is predicted in case of monodentate or bidentate (with the nitro group) bonding of the carbonyl C dbnd O group to the metal ion.

  12. Dynamics of ground and excited state vibrational relaxation and energy transfer in transition metal carbonyls.

    PubMed

    Delor, Milan; Sazanovich, Igor V; Towrie, Michael; Spall, Steven J; Keane, Theo; Blake, Alexander J; Wilson, Claire; Meijer, Anthony J H M; Weinstein, Julia A

    2014-10-09

    Nonlinear vibrational spectroscopy provides insights into the dynamics of vibrational energy transfer in and between molecules, a crucial phenomenon in condensed phase physics, chemistry, and biology. Here we use frequency-domain 2-dimensional infrared (2DIR) spectroscopy to investigate the vibrational relaxation (VR) and vibrational energy transfer (VET) rates in different solvents in both the electronic ground and excited states of Re(Cl)(CO)3(4,4'-diethylester-2,2'-bipyridine), a prototypical transition metal carbonyl complex. The strong C≡O and ester C═O stretch infrared reporters, located on opposite sides of the molecule, were monitored in the 1600-2100 cm(-1) spectral region. VR in the lowest charge transfer triplet excited state ((3)CT) is found to be up to eight times faster than in the ground state. In the ground state, intramolecular anharmonic coupling may be solvent-assisted through solvent-induced frequency and charge fluctuations, and as such VR rates are solvent-dependent. In contrast, VR rates in the solvated (3)CT state are surprisingly solvent-insensitive, which suggests that predominantly intramolecular effects are responsible for the rapid vibrational deactivation. The increased VR rates in the excited state are discussed in terms of intramolecular electrostatic interactions helping overcome structural and thermodynamic barriers for this process in the vicinity of the central heavy atom, a feature which may be of significance to nonequilibrium photoinduced processes observed in transition metal complexes in general.

  13. Carbonyl clusters of transition metals on oxide supports as heterogeneous catalysts for hydrocarbon synthesis

    SciTech Connect

    Kuznetsov, B.N.; Koval`chuk, V.I.

    1995-05-01

    The methods of preparation of heterogeneous catalysts by immobilization of carbonyl clusters of transition metals on oxide supports, as well as the study of the state of supported compounds and their catalytic properties in CO hydrogenation and olefin hydroformulation are briefly reviewed.

  14. [pi] Backbonding in Carbonyl Complexes and Carbon-Oxygen Stretching Frequencies: A Molecular Modeling Exercise

    ERIC Educational Resources Information Center

    Montgomery, Craig D.

    2007-01-01

    An exercise is described that has illustrated the effect of various factors on [pi] backbonding to carbonyl ligands, where the students can view the molecular orbitals corresponding to the M-CO [pi] interaction as well as the competing interaction between the metal and co-ligands. The visual and hands-on nature of the modeling exercise has helped…

  15. [pi] Backbonding in Carbonyl Complexes and Carbon-Oxygen Stretching Frequencies: A Molecular Modeling Exercise

    ERIC Educational Resources Information Center

    Montgomery, Craig D.

    2007-01-01

    An exercise is described that has illustrated the effect of various factors on [pi] backbonding to carbonyl ligands, where the students can view the molecular orbitals corresponding to the M-CO [pi] interaction as well as the competing interaction between the metal and co-ligands. The visual and hands-on nature of the modeling exercise has helped…

  16. Ring opening and carbonylation of 3,3-dimethylthietane ligands in ruthenium carbonyl cluster complexes

    SciTech Connect

    Adams, R.D.; Belinski, J.A.; Yamamoto, J.H.

    1992-10-01

    When heated to 97{degrees}C, the complex Ru{sub 4}(CO){sub 12}[{mu}-SCH{sub 2}CMe{sub 2}CH{sub 2}]2 (1) was transformed into two new hexaruthenium cluster complexes, Ru{sub 6}(CO){sub 13}({mu}{sub 3}-SCH{sub 2}CMe{sub 2}CH{sub 2}){sub 4} (2) and Ru{sub 6}(CO){sub 12}({mu}-SCH{sub 2}CMe{sub 2}CH{sub 2})({mu}{sub 3}-SCH{sub 2}CMe{sub 2}CH{sub 2}){sub 3}[{mu}{sub 3}-SCH{sub 2}C(Me)(CH{sub 2})CH{sub 2}] ({mu}-H) (3), that contain four and five ring-opened 3,3-dimethylthietane (3,3-DMT) ligands, respectively. In compound 3 one of the ring-opened DMT ligands has also undergone a CH activation on one of the methyl groups. Compound 2 reacts with additional 3,3-DMT at 97{degrees}C to form 3 in 18% yield. When treated with CO at 95{degrees}C (500 psi), compound 2 yielded 4,4-dimethylthiobutyrolactone and Ru{sub 3}(CO){sub 12}. It was also found that the complex Os{sub 3}(CO){sub 11-}(SCH{sub 2}CMe{sub 2}CH{sub 2}C{double_bond}O) (4) yields 4,4-dimethylthiobutyrolactone when treated with CO at 120{degrees}C (1200 psi). Crystal data for 2: space group P2{sub 1}/n, {alpha} = 22.652 (7) A, {beta} = 11.712 (2) A, c = 19.965 (6) A, {Beta} = 115.75 (2){degrees} Z = 4, 3665 reflections, R = 0.021. Crystal data for 3: space group P2{sub 1}/c, {alpha} = 17.332 (8) A, {Beta} = 14.668 (9) A, c = 19.823 (9) A, {Beta} = 91.27 (4){degrees}, Z = 4, 1875 reflections, R = 0.050. 13 refs., 2 figs., 13 refs.

  17. Luminescent property and catalytic activity of Ru(II) carbonyl complexes containing N, O donor of 2-hydroxy-1-naphthylideneimines

    NASA Astrophysics Data System (ADS)

    Sivagamasundari, M.; Ramesh, R.

    2007-05-01

    The reaction of the chelating ligands (obtained by the condensation of 2-hydroxy-1-naphthaldehyde with various primary amines) with [RuHCl(CO)(EPh 3) 2(B)] (where E = P; B = PPh 3, py or pip: E = As; B = AsPh 3) in benzene afforded new stable ruthenium(II) carbonyl complexes of the general formula [Ru(Cl)(CO)(EPh 3)(B)(L)] (L = anion of bidentate Schiff bases). The structure of the new complexes was investigated using elemental analyses, spectral (FT-IR, UV-vis and 1H NMR) and electrochemical studies and is found to be octahedral. All the metal complexes exhibit characteristic MLCT absorption and luminescence bands in the visible region. The luminescence efficiency of the ruthenium(II) complexes was explained based on the ligand environment around the metal ion. These complexes catalyze oxidation of primary and secondary alcohols into their corresponding carbonyl compounds in the presence of N-methylmorpholine- N-oxide (NMO) as the source of oxygen. The formation of high valent Ru IVdbnd O species as a catalytic intermediate is proposed for the catalytic process.

  18. The kinetics and mechanism of dissociation of metal carbonyls in high infrared laser fields

    NASA Astrophysics Data System (ADS)

    Langsam, Y.; Ronn, A. M.

    1981-01-01

    The method of laser induced dielectric breakdown has been used to study the dissociation of three metal carbonyls. Following non-resonant excitation by a TEA CO 2 laser, amorphous micro-metallic particles are deposited. The identity of the various species within a laser induced plasma for a series of related reactant molecules, has been determined using infrared and visible real time fluorescence techniques. Based upon the energetics of dissociation and the relative magnitudes of the rates of activation and deactivation for various collision partners of the plasma fluorescence, an energy transfer map as well as probable mechanisms are proposed. The kinetics of a variety of chemical reactions under plasma conditions are discussed in terms of elementary collision theory. It is shown that the internal vibration manifold of the metal carbonyls is equilibrated prior to the dissociation in agreement with the majority of laser induced multiphoton dissociation experiments.

  19. Oligocyclopentadienyl transition metal complexes

    SciTech Connect

    de Azevedo, Cristina G.; Vollhardt, K. Peter C.

    2002-01-18

    Synthesis, characterization, and reactivity studies of oligocyclopentadienyl transition metal complexes, namely those of fulvalene, tercyclopentadienyl, quatercyclopentadienyl, and pentacyclopentadienyl(cyclopentadienyl) are the subject of this account. Thermal-, photo-, and redox chemistries of homo- and heteropolynuclear complexes are described.

  20. Base assisted C-C coupling between carbonyl and polypyridyl ligands in a Ru-NADH-type carbonyl complex.

    PubMed

    Ghosh, Debashis; Fukushima, Takashi; Kobayashi, Katsuaki; Sen, Susan; Kitagawa, Susumu; Kato, Tatsuhisa; Tanaka, Koji

    2017-03-27

    A reaction of a ruthenium(ii) NAD-type complex, [Ru(tpy)(pbn)(Cl)](+) (tpy = 2,2':6',2''-terpyridine; pbn = 2-(pyridin-2-yl)benzo[b][1,5]naphthyridine), with pressurized CO (2 MPa) at 150 °C in H2O selectively produced a two-electron reduced ruthenium(ii)-NADH-type carbonyl complex, [Ru(tpy)(pbnHH)(CO)](2+) (pbnHH = 2-(pyridin-2-yl)-5,10-dihydrobenzo[b][1,5]naphthyridine), rather than the oxidized [Ru(tpy)(pbn)(CO)](2+) complex. Indeed, [Ru(tpy)(pbnHH)(CO)](2+) was quantitatively oxidized to [Ru(tpy)(pbn)(CO)](2+) upon treatment with one equiv. of 2,3-dichloro-5,6-dicyano-p-benzoquinone (DDQ). The reactivity of [Ru(tpy)(pbnHH)(CO)](2+) with various bases was studied herein. Treatment of [Ru(tpy)(pbnHH)(CO)](2+) with a suitable organic base, 1,5-diazabicyclo[4.3.0]non-5-ene (DBN), resulted in the formation of a new five-membered Ru-CO-bridge metallacycle quantitatively in acetonitrile under air at room temperature. A probable mechanism was proposed for this reaction based on UV-vis, NMR, and EPR spectral studies and other experimental data. Furthermore, a reaction of the five membered Ru-CO-bridge metallacycle with NH4PF6 in CH3CN : H2O (1 : 1) under air smoothly produced another new six-membered Ru-OCO-bridge complex. A mechanism for the formation of a Ru-OCO-bridge complex was also proposed here on the basis of H2O(18) experiments, DDQ treatment and other experimental data. These newly synthesized complexes appended with NAD-type ligands may have potential use as renewable hydride sources for organic reductions.

  1. Characterization of the temporary anion states of metal carbonyl complexes: an MS-X. cap alpha. and ETS study of Cr(CO)/sub 6/ and Fe(CO)/sub 5/

    SciTech Connect

    Guerra, M.; Jones, D.; Distefano, G.; Foffani, A.; Modelli, A.

    1988-01-20

    The electron affinities in the 0-5 eV energy range have been determined for chromium hexacarbonyl and iron pentacarbonyl by means of multiple scattering X..cap alpha.. calculations. The total electron scattering cross sections have been estimated with the continuum MS-X..cap alpha.. method. The computational results are compared with the electron transmission spectra and used for the assignment of the experimental features. The ET spectrum of Fe(CO)/sub 5/ is presented and assigned for the first time and that of Cr(CO)/sub 6/ is reassigned. For both complexes, all the anion states associated with electron capture into the orbitals deriving from the ligand 2..pi..* MOs and into the metal empty d orbitals are assigned to resonances occurring in the 0.4-2.6 eV energy region of the ET spectra. A charge density analysis reveals that a net electronic charge transfer occurs from the ligands to the metal, owing to the acceptor capability of the metal 4s and 4p orbitals. This is consistent with the experimentally observed average stabilization of the anion states localized at the CO ligands with respect to the II anion state of free CO.

  2. New group 6 metal carbonyl complexes with 4,5-dimethyl-N,N-bis(pyridine-2-yl-methylene)benzene-1,2-diimine Schiff base: synthesis, spectral, cyclic voltammetry and biological activity studies.

    PubMed

    Mohamed, Rania G; Elantabli, Fatma M; Helal, Nadia H; El-Medani, Samir M

    2015-04-15

    Thermal reaction of M(CO)6 (M=Cr, Mo or W) with a Schiff base (DMPA) derived from the condensation of 4,5-dimethyl-1,2-phenylenediamine and pyridine-2-carboxaldehyde in THF in absence and presence of a secondary ligand; 2-aminobenzimidazole (Abz), thiourea (Tu) or 2-(2'-pyridyl)benzimidazole (pybz) were studied. The reaction of Cr(CO)6 gave the four complexes Cr2(CO)2(DMPA)2; 1, Cr(DMPA)2(Abz)2; 2, Cr2(CO)4(DMPA)2(Tu)2; 3 and Cr(DMPA)2(Pybz); 4, while the thermal reaction of Mo(CO)6 resulted in the formation of the two complexes Mo2(O)6(DMPA)2; 5, and Mo2(O)2(CO)2(DMPA)2(Tu)2; 6. Thermal reaction of W(CO)6 and the Schiff base DMPA gave the complex W(O)2(DMPA)2; 7. The ligand DMPA and its metal complexes have been reported and characterized based on elemental analyses, IR, (1)H NMR, magnetic measurements, and thermal analysis. Cyclic voltammetry and biological activity were also investigated. Copyright © 2015 Elsevier B.V. All rights reserved.

  3. New group 6 metal carbonyl complexes with 4,5-dimethyl-N,N-bis(pyridine-2-yl-methylene)benzene-1,2-diimine Schiff base: Synthesis, spectral, cyclic voltammetry and biological activity studies

    NASA Astrophysics Data System (ADS)

    Mohamed, Rania G.; Elantabli, Fatma M.; Helal, Nadia H.; El-Medani, Samir M.

    2015-04-01

    Thermal reaction of M(CO)6 (M = Cr, Mo or W) with a Schiff base (DMPA) derived from the condensation of 4,5-dimethyl-1,2-phenylenediamine and pyridine-2-carboxaldehyde in THF in absence and presence of a secondary ligand; 2-aminobenzimidazole (Abz), thiourea (Tu) or 2-(2‧-pyridyl)benzimidazole (pybz) were studied. The reaction of Cr(CO)6 gave the four complexes Cr2(CO)2(DMPA)2; 1, Cr(DMPA)2(Abz)2; 2, Cr2(CO)4(DMPA)2(Tu)2; 3 and Cr(DMPA)2(Pybz); 4, while the thermal reaction of Mo(CO)6 resulted in the formation of the two complexes Mo2(O)6(DMPA)2; 5, and Mo2(O)2(CO)2(DMPA)2(Tu)2; 6. Thermal reaction of W(CO)6 and the Schiff base DMPA gave the complex W(O)2(DMPA)2; 7. The ligand DMPA and its metal complexes have been reported and characterized based on elemental analyses, IR, 1H NMR, magnetic measurements, and thermal analysis. Cyclic voltammetry and biological activity were also investigated.

  4. The Spectroscopy and Reaction Kinetics of Coordinated Unsaturated Metal Carbonyls.

    DTIC Science & Technology

    1985-10-20

    liquid disso- ciation. I. Martyn Poliakoff and Eric Weitz, to be published in "Advances in Organo- metallic Chemistry" (1985). 2. A. J. Ouderkirk, P... Poliakoff and Eric Weitz, to be published in Annual Review of Organometallic Chemistry, 1985. c) Gas Phase Infrared Spectroscopy and Recombination Kinetics...support of this work by the 7.. 7 donors of the Petroleum Research Fund, administered by the American Chemical * -Society. We thank Dr. Martyn Poliakoff

  5. The reactions of Cr(CO)6, Fe(CO)5, and Ni(CO)4 with O2 yield viable oxo-metal carbonyls.

    PubMed

    Sun, Zhi; Schaefer, Henry F; Xie, Yaoming; Liu, Yongdong; Zhong, Rugang

    2014-05-15

    Transition metal complexes with terminal oxo and dioxygen ligands exist in metal oxidation reactions, and many are key intermediates in various catalytic and biological processes. The prototypical oxo-metal [(OC)5Cr-O, (OC)4Fe-O, and (OC)3 Ni-O] and dioxygen-metal carbonyls [(OC)5Cr-OO, (OC)4Fe-OO, and (OC)3Ni-OO] are studied theoretically. All three oxo-metal carbonyls were found to have triplet ground states, with metal-oxo bond dissociation energies of 77 (Cr-O), 74 (Fe-O), and 51 (Ni-O) kcal/mol. Natural bond orbital and quantum theory of atoms in molecules analyses predict metal-oxo bond orders around 1.3. Their featured ν(MO, M = metal) vibrational frequencies all reflect very low IR intensities, suggesting Raman spectroscopy for experimental identification. The metal interactions with O2 are much weaker [dissociation energies 13 (Cr-OO), 21 (Fe-OO), and 4 (Ni-OO) kcal/mol] for the dioxygen-metal carbonyls. The classic parent compounds Cr(CO)6, Fe(CO)5, and Ni(CO)4 all exhibit thermodynamic instability in the presence of O2 , driven to displacement of CO to form CO2. The latter reactions are exothermic by 47 [Cr(CO)6], 46 [Fe(CO)5], and 35 [Ni(CO)4] kcal/mol. However, the barrier heights for the three reactions are very large, 51 (Cr), 39 (Fe), and 40 (Ni) kcal/mol. Thus, the parent metal carbonyls should be kinetically stable in the presence of oxygen. Copyright © 2014 Wiley Periodicals, Inc.

  6. NEW REACTIONS OF METAL CARBONYLS AND RELATED COMPOUNDS.

    DTIC Science & Technology

    or M (IV)R3 where M(IV) = Si, Ge or Sn, and R = Et, Ph or Cl. The results are used to draw certain conclusions about the nature of the Fe-X bond. Part II of the Report describes the synthesis of new tin-ruthenium complexes of type (R3Sn)2Ru(CO)4 and R10Sn4Ru2(CO)6. Part III gives an account of the preparation of silicon-ruthenium compounds (R3SiRu(CO)4)2, particularly (Me3SiRu(CO)4)2. The latter complex has proved to be an important intermediate for further syntheses. The work on the silicon-ruthenium complexes is still at a preliminary stage and further work needs to

  7. Ru and Os film deposition from metal carbonyls

    SciTech Connect

    Berry, A.D.; Brown, D.J.; Kaplan, R.; Cukauskas, E.J.

    1986-03-01

    Adherent, highly reflective films of Ru and Os have been deposited in vacuum on heated Si substrates by thermal decomposition of the pentacarbonyls Ru(CO)/sub 5/ and Os(CO)/sub 5/, at 150 and 200 /sup 0/C, respectively. Auger analysis after ion bombardment cleaning revealed nearly O-free surfaces, with slight C contamination which grew with exposure to the primary electron beam, thus making accurate determination of C content difficult. X-ray diffraction showed the films to be polycrystalline with the expected hexagonal close-packed structure, while measured resistivities were about a factor of 3 greater than bulk values. This method of depositing Ru and Os offers the advantages of simplicity, modest temperature requirement, and metallization of heated surfaces only.

  8. ansa-Chromocene complexes. 1. Synthesis and characterization of Cr(II) carbonyl and tert-butyl isocyanide complexes

    SciTech Connect

    Matare, G.J.; Foo, D.M.; Kane, K.M.; Zehnder, R.; Wagener, M.; Shapiro, P.J.; Concolino, T.; Rheingold, A.L.

    2000-04-17

    ansa-Calcocene compounds are effective reagents for the synthesis of ansa-chromocene complexes from CrCl{sub 2} in the presence of a trapping ligand such as carbon monoxide or an isonitrile. A variety of ansa-chromocene carbonyl and tert-butyl isocyanide complexes have been prepared in this manner in high yields. The X-ray crystal structure of one of these complexes, [trans-1,2-(3,4-(CH{sub 3}O){sub 2}C{sub 6}H{sub 3}){sub 2}C{sub 2}H{sub 2}{l_brace}{eta}{sup 5}-C{sub 5}H{sub 4}{r_brace}{sub 2}]CrCO, is described. Electrochemical studies on these complexes show that the isonitrile derivatives are more easily oxidized than the carbonyl derivatives. Preliminary examination of the reactivity of these complexes indicates that the nature of the substitution along the ethanediyl ansa-bridge influences the relative stabilities of the carbonyl complexes to oxidation in air, the ease with which the carbonyl ligands undergo substitution with tert-butyl isocyanide, and the relative sensitivities of the tert-butyl isocyanide adducts to photodecomposition. The ansa-bridge substitution also appears to influence the ability of the complexes to undergo structural changes, such as ring slippage, as revealed in their cyclic voltammograms.

  9. Photochemical carbonylation of benzene by iridium(I) and rhodium(I) square-planar complexes

    SciTech Connect

    Kunin, A.J.; Eisenberg, R.

    1988-10-01

    The photochemical carbonylation of unfunctionalized arene C-H bonds is catalyzed by various d/sup 8/ complexes under low CO pressure at ambient temperature. The carbonylation of benzene to benzaldehyde is achieved by using IrH(CO)/sub 2/(dppe), IrH/sub 3/(CO)(dppe), or IrBr(CO)(dppe) as the catalyst, and the photoactive species in each case appears to be IrX(CO)(dppe) (X = H or Br). The monodentate phosphine complexes MCl(CO)(PPh/sub 3/)/sub 2/ (M = Rh, Ir) exhibit similar photochemical activity leading to benzene carbonylation. In all cases the amount of benzaldehyde formed is limited by thermodynamics with /Delta/G/sub 298//degree/ = +1.7 kcal. When RhCl(CO)(PPh/sub 3/)/sub 2/ is placed under /sup 13/CO with PhCHO, photochemical decarbonylation is achieved along with significant /sup 13/CO incorporation into the aldehyde, confirming the occurrence of both carbonylation and decarbonylation. Both processes are thought to involve the same initial photochemical step of ligand dissociation to generate a 14e intermediate.

  10. Chemistry of carbonyl sulfide. Final report, 1 July 1983-30 June 1984. [Lanthanide complexes of monothiocarbamates

    SciTech Connect

    Hinkley, C.C.; Dunkerton, L.V.; Tyrell, J.

    1984-01-01

    This report details research into the chemical properties ad structure of carbonyl sulfide, COS. Lanthanide complexes of monothiocarbamates have been prepared and investigations of displacement reactions begun. Diels-adler reactions of COS have been investigated as have COS ene reactions. Theoretical calculations of the structures of COS-metal complexes have been performed. These calculations indicate a preference for bonding by Ti and Fe to the oxygen end of COs forming a linear complex. In the case of nickel, bonding is to the C-S bond. In all cases the C-S bond is substantially lengthened, suggesting resultant elimination of sulfur. Additional calculations have been carried out on H/sub 4/Ti(COS), Ti(OCO), Ti(SCS), and Ti(H/sub 2/S), but only preliminary results are available on these systems. 10 references, 2 figures, 4 tables.

  11. Catalytic Addition of Simple Alkenes to Carbonyl Compounds Using Group 10 Metals

    PubMed Central

    Schleicher, Kristin D.

    2011-01-01

    Recent advances using nickel complexes in the activation of unactivated monosubstituted olefins for catalytic intermolecular carbon–carbon bond-forming reactions with carbonyl compounds, such as simple aldehydes, isocyanates, and conjugated aldehydes and ketones, are discussed. In these reactions, the olefins function as vinyl- and allylmetal equivalents, providing a new strategy for organic synthesis. Current limitations and the outlook for this new strategy are also discussed. PMID:21904421

  12. Unsaturated binuclear cyclopentadienylrhenium carbonyl derivatives: metal-metal multiple bonds and agostic hydrogen atoms.

    PubMed

    Xu, Bing; Li, Qian-shu; Xie, Yaoming; King, R Bruce; Schaefer, Henry F

    2008-08-04

    The cyclopentadienylrhenium carbonyls Cp 2Re 2(CO) n (Cp = eta (5)-C 5H 5; n = 5, 4, 3, 2) have been studied by density functional theory. The global minima for the Cp 2Re 2(CO) n ( n = 5, 4, 3, 2) derivatives are predicted to be the singly bridged structure Cp 2Re 2(CO) 4(mu-CO) with a formal Re-Re single bond; the doubly semibridged structure Cp 2Re 2(CO) 4 with a formal ReRe double bond; the triply bridged structure Cp 2Re 2(mu-CO) 3 with a formal ReRe triple bond; and the doubly bridged structure Cp 2Re 2(mu-CO) 2, respectively. The first three of these predicted structures have been realized experimentally in the stable compounds (eta (5)-C 5H 5) 2Re 2(CO) 4(mu-CO), (eta (5)-Me 5C 5) 2Re 2(CO) 4 and (eta (5)-Me 5C 5) 2Re 2(mu-CO) 3. In addition, structures of the type Cp 2Re-Re(CO) n with both rings bonded only to one metal and unknown in manganese chemistry are also found for rhenium but at energies significantly above the global minima. The unsaturated Cp 2Re-Re(CO) n structures ( n = 4, 3, 2) have agostic Cp hydrogen atoms forming C-H-Re bridges to the unsaturated Re(CO) n group with a Re-H distance as short as 2.04 A.

  13. Electron beam induced surface nucleation and low temperature thermal decomposition of metal carbonyls

    NASA Astrophysics Data System (ADS)

    Kunz, R. R.; Mayer, T. M.

    1988-09-01

    Selective area deposition of iron, chromium, and tungsten thin films via thermal decomposition of their respective carbonyls has been performed on electron beam deposited pre-nucleated layers. The prenucleated layers were deposited either by gas phase or surface electron induced dissociation of the respective carbonyl, depending on the chemical system and operating conditions used. The presence of this layer effectively lowers the activation energy for the decomposition event. The activation energies for the decomposition of the metal carbonyls on their respective prenucleated layers were measured over the temperature range 125 to 350 C and found to be lower than for decomposition on clean silicon. The kinetics of formation of the prenucleated layers were measured over the temperature range 125 to 350 C and found to be lower than for decomposition on clean silicon. The kinetics of formation of the prenucleated layers were measured over the temperature range 125 to 350 C and found to be lower than for decomposition on clean silicon. The kinetics of formation of the prenucleated layer suggest that the formation of stable nuclei is dependent on the rate of desorption of CO from the surface. Electron stimulated desorption of CO is proposed as the mechanism for production of nuclei at low temperature by electron bombardment. Structure and composition of the nucleated layer and deposited film were examined by TEM, SEM, AES, and EDX.

  14. Photon-Induced Thermal Desorption of CO from Small Metal-Carbonyl Clusters

    NASA Astrophysics Data System (ADS)

    Lüttgens, G.; Pontius, N.; Bechthold, P. S.; Neeb, M.; Eberhardt, W.

    2002-02-01

    Thermal CO desorption from photoexcited free metal-carbonyl clusters has been resolved in real time using two-color pump-probe photoelectron spectroscopy. Sequential energy dissipation steps between the initial photoexcitation and the final desorption event, e.g., electron relaxation and thermalization, have been resolved for Au2(CO)- and Pt2(CO)-5. The desorption rates for the two clusters differ considerably due to the different numbers of vibrational degrees of freedom. The unimolecular CO-desorption thresholds of Au2(CO)- and Pt2(CO)-5 have been approximated by means of a statistical Rice-Ramsperger-Kassel calculation using the experimentally derived desorption rate constants.

  15. A halogenophilic pathway in the reactions of transition metal carbonyl anions with [(η⁶-iodobenzene)Cr(CO)₃].

    PubMed

    Sazonov, Petr K; Ivushkin, Vasiliy A; Khrustalev, Victor N; Kolotyrkina, Natal'ya G; Beletskaya, Irina P

    2014-09-21

    The paper provides the first example of formal nucleophilic substitution by the halogenophilic pathway in Cr(CO)3 complexes of haloarenes with metal carbonyl anions. All metal carbonyl anions examined attack [(η(6)-iodobenzene)Cr(CO)3] at halogen, which is shown by aryl carbanion scavenging with t-BuOH. The reaction with K[CpFe(CO)2] gives only the dehalogenated arene, but the reaction with K[Cp*Fe(CO)2] (Cp* = η(5)-C5Me5) results in nucleophilic substitution to give [(η(6)-C6H5FeCp*(CO)2)Cr(CO)3]. Reaction with Na[Re(CO)5] quantitatively gives the iodo(acyl)rhenate anion Na[(η(6)-C6H5C(O)ReI(CO)4)Cr(CO)3] and in the case of K[Mn(CO)5] a mixture of σ-aryl complexes [(η(6)-C6H5Mn(CO)5)Cr(CO)3] and K[(η(6)-C6H5Mn(CO)4I)Cr(CO)3]. An analogous rhenium complex Na[(η(6)-C6H5Re(CO)4I)Cr(CO)3] is formed from the initial iodo(acyl)rhenate upon prolonged standing at 20 °C, and its structure (in the form of [NEt4](+) salt) is established by X-ray diffraction analysis. The reaction of [(η(6)-chlorobenzene)Cr(CO)3] with K[CpFe(CO)2], in contrast, proceeds by the common S(N)2Ar mechanism.

  16. VCD spectroscopy as an excellent probe of chiral metal complexes containing a carbon monoxide vibrational chromophore.

    PubMed

    Fusè, Marco; Mazzeo, Giuseppe; Longhi, Giovanna; Abbate, Sergio; Zerla, Daniele; Rimoldi, Isabella; Contini, Alessandro; Cesarotti, Edoardo

    2015-06-07

    Vibrational circular dichroism, VCD, gives evidence that the carbon monoxide chromophore in a heteroleptic cyclopentadienyl Ru(ii)-carbonyl complex is very sensitive to the chirality of the metal centre and becomes an excellent probe to define the configuration of chiral metal complexes.

  17. Spectra structure correlations in solid metal saccharinates. I. The carbonyl stretchings

    NASA Astrophysics Data System (ADS)

    Naumov, P.; Jovanovski, G.

    2001-05-01

    Results from literature survey of the infrared carbonyl stretching bands of 73 solid saccharinates, saccharin and the saccharinato nitranion (the latter in diluted DMSO solution) are presented. The CO frequencies are correlated with the C-O and metal-saccharinato distances and the respective formal bond orders. The present survey reveals that occasionally some ν(CO) frequencies in the spectra of saccharinates may be higher than that of saccharin (1725 cm -1) indicating existence of molecular saccharin in the respective structures. Due to intra- and intermolecular reasons, often the numbers of ν(CO) bands and structural types of CO groups do not coincide. Presumably due to both vibrational and structural factors, saccharinato ν(CO) frequencies are not advantageous for very accurate prediction of the C-O and metal-saccharinato distances. Nevertheless, they can be used as a qualitative criterion for evaluation of the degree of covalency of metal-saccharinato bonding as well as for very approximate estimation of the C-O distances and metal-saccharinato bond orders.

  18. On the structure and bonding of first row transition metal ozone carbonyl hydrides.

    PubMed

    Venter, Gerhard A; Raubenheimer, Helgard G; Dillen, Jan

    2007-08-23

    Model complexes of the general form M(CO)m(H)n(O3) (m = 1-5, n = 0 or 1) between ozone and the transition metals Ti to Cu were studied by density functional theory (DFT) calculations. The CDA charge decomposition method was used to analyze the interaction between the metal atom and the ozone ligand in terms of the traditional donation-back-donation mechanisms. Information about bond strengths was extracted from an analysis of the electron density in terms of the theory of atoms in molecules (AIM). The bonding in the ozone-metal complex was also studied within the NBO paradigm. Bond dissociation energies were calculated to be positive for all the complexes studied. Considering all the criteria employed in this study to analyze the interaction between the ozone and the transition metal, the Fe-complex is predicted to be the most stable, whereas the copper complex has the weakest metal-ozone interaction.

  19. Selenophene transition metal complexes

    SciTech Connect

    White, Carter James

    1994-07-27

    This research shows that selenophene transition metal complexes have a chemistry that is similar to their thiophene analogs. Selenophene coordination has been demonstrated and confirmed by molecular structure in both the η5- and the η1(Se)-coordination modes. The reaction chemistry of selenophene complexes closely resembles that of the analogous thiophene complexes. One major difference, however, is that selenophene is a better donor ligand than thiophene making the selenophene complexes more stable than the corresponding thiophene complexes. The 77Se NMR chemical shift values for selenophene complexes fall within distinct regions primarily depending on the coordination mode of the selenophene ligand. In the final paper, the C-H bond activation of η1(S)-bound thiophenes, η1(S)-benzothiophene and η1(Se)-bound selenophenes has been demonstrated. The deprotonation and rearrangement of the η1(E)-bound ligand to the carbon bound L-yl complex readily occurs in the presence of base. Reprotonation with a strong acid gives a carbene complex that is unreactive towards nucleophilic attack at the carbene carbon and is stable towards exposure to air. The molecular structure of [Cp(NO)(PPh3)Re(2-benzothioenylcarbene)]O3SCF3 was determined and contains a Re-C bond with substantial double bond character. Methyl substitution for the thienylcarbene or selenylcarbene gives a carbene that rearranges thermally to give back the η1(E)-bound complex. Based on these model reactions, a new mechanism for the H/D exchange of thiophene over the hydrodesulfurization catalyst has been proposed.

  20. Reactivity of a Ruthenium–Carbonyl Complex in the Methanol Dehydrogenation Reaction

    PubMed Central

    van de Watering, Fenna F.; Lutz, Martin; Dzik, Wojciech I.; de Bruin, Bas

    2016-01-01

    Abstract Finding new catalysts for the release of molecular hydrogen from methanol is of high relevance in the context of the development of sustainable energy carriers. Herein, we report that the ruthenium complex Ru(salbinapht)(CO)(Pi‐Pr3) {salbinapht=2‐[({2′‐[(2‐hydroxybenzyl)amino]‐[1,1′‐binaphthalen]‐2‐yl}imino)methyl]phenolato} (2) catalyzes the methanol dehydrogenation reaction in the presence of base and water to yield H2, formate, and carbonate. Dihydrogen is the only gas detected and a turnover frequency up to 55 h−1 at 82 °C is reached. Complex 2 bears a carbonyl ligand that is derived from methanol, as is demonstrated by labeling experiments. The carbonyl ligand can be treated with base to form formate (HCOO−) and hydrogen. The nature of the active species is further shown not to contain a CO ligand but likely still possesses a salen‐derived ligand. During catalysis, formation of Ru(CO)2(H)2(P‐iPr3)2 is occasionally observed, which is also an active methanol dehydrogenation catalyst. PMID:27917245

  1. Synthesis, electronic structure and catalytic activity of ruthenium-iodo-carbonyl complexes with thioether containing NNS donor ligand

    NASA Astrophysics Data System (ADS)

    Jana, Subrata; Jana, Mahendra Sekhar; Biswas, Sujan; Sinha, Chittaranjan; Mondal, Tapan Kumar

    2014-05-01

    The ruthenium carbonyl complexes 1 and 2 with redox noninnocent NNS donor ligand, 1-methyl-2-{(o-thiomethyl)phenylazo}imidazole (L) have been synthesized and characterized by various analytical and spectroscopic (IR, UV-Vis and 1H NMR) techniques. The complexes exhibit a quasi-reversible one electron Ru(II)/Ru(III) oxidation couple at 1.11 V for 1 and 0.76 V for 2 along with two successive one electron ligand reductions. Catalytic activity of the compounds has been investigated to the oxidation of PhCH2OH to PhCHO, 2-butanol (C4H9OH) to 2-butanone, 1-phenylethanol (PhC2H4OH) to acetophenone, cyclopentanol (C5H9OH) to cyclopentanone, cyclohexanol to cyclohexanone, cycloheptanol to cycloheptanone and cycloctanol to cycloctanone using N-methylmorpholine-N-oxide (NMO) as oxidant. The catalytic efficiency of 2 is greater than complex 1 and well correlate with the metal oxidation potential. DFT, NBO and TDDFT calculations in DFT/B3LYP/6-31G(d)/lanL2TZ(f) method are employed to interpret the structural and electronic features of the complexes.

  2. Synthesis, characterization, electronic structure and catalytic activity of new ruthenium carbonyl complexes of N-[(2-pyridyl)methylidene]-2-aminothiazole

    NASA Astrophysics Data System (ADS)

    Kundu, Subhankar; Sarkar, Deblina; Jana, Mahendra Sekhar; Pramanik, Ajoy Kumar; Jana, Subrata; Mondal, Tapan Kumar

    2013-03-01

    Reaction of ruthenium carbonyls, [Ru(CO)2Cl2]n/[Ru(CO)4I2] with bidentate Schiffs base ligands derived by the condensation of pyridine-2-carboxaldehyde with 2-aminothiazole in a 1:1 mole ratio in acetonitrile led to the formation of complexes having general formula [Ru(CO)2(L)X2] (X = Cl (1) and I (2)) (L = N-[(2-pyridyl)methylidene]-2-aminothiazole). The compounds have been characterized by various analytical and spectroscopic (IR, electronic and 1H NMR) studies. In acetonitrile solution the complexes exhibit a weak broad metal-ligand to ligand charge transfer (MLLCT) band along with ILCT transitions. The compounds are emissive in room temperature upon excitation in the ILCT band. The complexes exhibit a quasi-reversible one electron Ru(II)/Ru(III) oxidation couple at 1.44 V for 1 and 0.94 V for 2. Catalytic activity of these compounds is investigated to the oxidation of PhCH2OH to PhCHO, 2-butanol (C4H9OH) to 2-butanone, 1-phenylethanol (PhC2H4OH) to acetophenone, cyclopentanol (C5H9OH) to cyclopentanone, cyclohexanol to cyclohexanone, cycloheptanol to cycloheptanone and cycloctanol to cycloctanone using N-methylmorpholine-N-oxide (NMO) as oxidant. The catalytic efficiency of 2 is greater than complex 1 and well correlate with the metal oxidation potential of the complexes. DFT, NBO and TDDFT calculations are employed to explain the structural and electronic features and to support the spectroscopic assignments.

  3. Transition-Metal-Catalyzed C-H Bond Addition to Carbonyls, Imines, and Related Polarized π Bonds.

    PubMed

    Hummel, Joshua R; Boerth, Jeffrey A; Ellman, Jonathan A

    2016-12-12

    The transition-metal-catalyzed addition of C-H bonds to carbonyls, imines, and related polarized π bonds has emerged as a particularly efficient and powerful approach for the construction of an incredibly diverse array of heteroatom-substituted products. Readily available and stable inputs are typically employed, and reactions often proceed with very high functional group compatibility and without the production of waste byproducts. Additionally, many transition-metal-catalyzed C-H bond additions to polarized π bonds occur within cascade reaction sequences to provide rapid access to a diverse array of different heterocyclic as well as carbocyclic products. This review highlights the diversity of transformations that have been achieved, catalysts that have been used, and types of products that have been prepared through the transition-metal-catalyzed addition of C-H bonds to carbonyls, imines, and related polarized π bonds.

  4. CO(v=1) population lifetimes of metal-carbonyl cluster compounds in dilute CHCl3 solution

    NASA Astrophysics Data System (ADS)

    Heilweil, E. J.; Cavanagh, R. R.; Stephenson, J. C.

    1988-07-01

    Tunable infrared picosecond pulses in the 5 μ region have been used for time-resolved pump-probe measurements of the population relaxation lifetime (T1) of CO(v=1) stretching vibrations in a series of metal-carbonyl cluster compounds in room temperature chloroform solution. T1 was the same for symmetric (ν=2084 cm-1, 90±10 ps) and antisymmetric (2014 cm-1, 87±10 ps) modes of the dicarbonyl Rh(CO)2(C5H7O2); T1 was the same for the B1 (2092 cm-1, 710±130 ps) and B2 (2036 cm-1, 750±90 ps) modes of Rh2(CO)4Cl2. Similarly long T1 times were found for Rh4(CO)12 (2075 cm-1, 610±65 ps) and Rh6(CO)16 (2077 cm-1, 700±100 ps). The molecule Co4(CO)12 has also been compared to the corresponding rhodium analog and it exhibits an initially fast relaxation of 47±5 ps followed by a slower 396±70 ps decay. The transient response of the more complex systems to the single frequency experiment is found to be sensitive to frequency and can exhibit bleaching, absorption, and a combination of these effects. Such behavior is attributed to overlap of the IR pulse with v=1 to v=2 and higher transitions in the M4(CO)12 (M=Rh or Co) and Rh6(CO)16 molecules. The long CO(v=1) T1 values for the metal cluster molecules suggest relaxation via multiquantum transfer of vibrational energy to adjacent M-C stretch and M-C-O bend vibrations; energy transfer to vibrational or electronic states of the central metal core seems unimportant in determining T1 for these systems.

  5. The metal-carbonyl bond in Ni(CO)4 and Fe(CO)5 - A clear-cut analysis

    NASA Technical Reports Server (NTRS)

    Bauschlicher, C. W., Jr.; Bagus, P. S.

    1984-01-01

    A detailed analysis of the metal-carbonyl bonding in Ni(CO)4 and Fe(CO)5, based on the newly developed contained space orbital variation (CSOV) method, is carried out to investigate various contributing factors to the interaction. Three aspects about the metal-CO interaction are presented: (1) the frozen orbital repulsion between the metal 4s and the CO is large; (2) the metal to CO pi donation is energetically much more important than the CO to the metal sigma donation; and (3) the metal 4s and 4p orbitals make a very small contribution (smaller than 0.4 eV) to the interaction energy; the largest portion of this contribution arises from the CO to metal sigma donation.

  6. A monotonic increase of formal metal-metal bond orders from one to five upon loss of carbonyl groups from binuclear benzene chromium carbonyls

    NASA Astrophysics Data System (ADS)

    Wang, Hui; Wang, Hongyan; Sun, Zhong-Hua; King, R. Bruce

    2013-06-01

    Benzene forms a binuclear chromium carbonyl derivative (η6-C6H6)2Cr2(μ-CO)3, shown by X-ray crystallography to have a very short Crtbnd Cr distance, suggesting the formal triple bond required to give each chromium atom the favored 18-electron configuration. We now describe theoretical studies on the entire series of binuclear benzene chromium carbonyls (C6H6)2Cr2(CO)n (n = 5, 4, 3, 2, 1). The predicted Cr-Cr distances in the lowest energy singlet structures determined by the BP86 method decrease monotonically as carbonyl groups are lost starting from 2.95 Å in (C6H6)2Cr2(CO)5 to 1.95 Å in (C6H6)2Cr2(CO) corresponding to a steady increase in the formal bond order from one to five. This increase in formal Cr-Cr bond order is also supported by a monotonic increase in the Wiberg bond indices ranging from 0.29 for the single bond in (C6H6)2Cr2(CO)5 to ˜2 for the formal quintuple bond in (C6H6)2Cr2(CO).

  7. Theoretical studies of the transition metal-carbonyl systems MCO and M(CO)2, M = Ti, Sc, and V

    NASA Technical Reports Server (NTRS)

    Barnes, Leslie A.; Bauschlicher, Charles W., Jr.

    1989-01-01

    Large Gaussian basis sets and an electron correlation treatment are used in ab initio calculations on the transition metal-carbonyl systems MCO and N(CO)2 for M = Ti, Sc, and V. The results show that high-spin ground states are favored for the monocarbonyl molecules, and that for the dicarbonyl molecules there is a competition between high, intermediate, and low spin states which are very close in energy. Dissociation energies of 0.62 eV for Ti-CO and 1.02 for Ti(CO)2 are found, relative to the ground state Ti atomic asymptote and CO 1Sigma(+). The binding energy per carbonyl for the three metal atoms is shown to be significantly lower for the dicarbonyl than for the the monocarbonyl molecules.

  8. The Quest for Metal-Metal Quadruple and Quintuple Bonds in Metal Carbonyl Derivatives: Nb2(CO)9 and Nb2(CO)8.

    PubMed

    Tang, Lihong; Luo, Qiong; Li, Qian-Shu; Xie, Yaoming; King, R Bruce; Schaefer, Henry F

    2012-03-13

    The synthesis by Power and co-workers of the first metal-metal quintuple bond (Science2005, 310, 844) is a landmark in inorganic chemistry. The 18-electron rule suggests that Nb2(CO)9 and Nb2(CO)8 are candidates for binary metal carbonyls containing metal-metal quadruple and quintuple bonds, respectively. Density functional theory (MPW1PW91 and BP86) indeed predicts structures having very short Nb-Nb distances of ∼2.5 Å for Nb2(CO)9 and ∼2.4 Å for Nb2(CO)8 as well as relatively large Nb-Nb Wiberg bond indices supporting these high formal Nb-Nb bond orders. However, analysis of the frontier molecular orbitals of these unbridged structures suggests formal Nb≡Nb triple bonds and 16-electron metal configurations. This contrasts with an analysis of the frontier orbitals in a model chromium(I) alkyl linear CH3CrCrCH3, which confirms the generally accepted presence of chromium-chromium quintuple bonds in such molecules. The presence of Nb≡Nb triple bonds rather than quadruple or quintuple bonds in the Nb2(CO)n (n = 9, 8) structures frees up d(xy) and d(x(2)-y(2)) orbitals for dπ→pπ* back-bonding to the carbonyl groups. The lowest energy Nb2(CO)n structures (n = 9, 8) are not these unbridged structures but structures having bridging carbonyl groups of various types and formal Nb-Nb orders no higher than three. Thus, the two lowest energy Nb2(CO)9 structures have Nb≡Nb triple bond distances of ∼2.8 Å and three semibridging carbonyl groups, leading to a 16-electron configuration rather than an 18-electron configuration for one of the niobium atoms. The lowest energy structure of the highly unsaturated Nb2(CO)8 is unusual since it has a formal single Nb-Nb bond of length ∼3.1 Å and two four-electron donor η(2)-μ-CO groups, thereby giving each niobium atom only a 16-electron configuration.

  9. Photoelectron velocity-map imaging and theoretical studies of heteronuclear metal carbonyls MNi(CO)3(-) (M = Mg, Ca, Al).

    PubMed

    Xie, Hua; Zou, Jinghan; Yuan, Qinqin; Fan, Hongjun; Tang, Zichao; Jiang, Ling

    2016-03-28

    The heteronuclear metal carbonyl anions MNi(CO)3(-) (M = Mg, Ca, Al) have been investigated using photoelectron velocity-map imaging spectroscopy. Electron affinities of neutral MNi(CO)3 (M = Mg, Ca, Al) are measured from the photoelectron spectra to be 1.064 ± 0.063, 1.050 ± 0.064, and 1.541 ± 0.040 eV, respectively. The C-O stretching mode in these three clusters is observed and the vibrational frequency is determined to be 2049, 2000, and 2041 cm(-1) for MgNi(CO)3, CaNi(CO)3, and AlNi(CO)3, respectively. Density functional theory calculations are carried out to elucidate the geometric and electronic structures and to aid the experimental assignments. It has been found that three terminal carbonyls are preferentially bonded to the nickel atom in these heterobinuclear nickel carbonyls MNi(CO)3 (-1/0), resulting in the formation of the Ni(CO)3 motif. Ni remains the 18-electron configuration for MgNi(CO)3 and CaNi(CO)3 neutrals, but not for AlNi(CO)3. This is different from the homobinuclear nickel carbonyl Ni-Ni(CO)3 with the involvement of three bridging ligands. Present findings would be helpful for understanding CO adsorption on alloy surfaces.

  10. Metal carbonyl vapor generation coupled with dielectric barrier discharge to avoid plasma quench for optical emission spectrometry.

    PubMed

    Cai, Yi; Li, Shao-Hua; Dou, Shuai; Yu, Yong-Liang; Wang, Jian-Hua

    2015-01-20

    The scope of dielectric barrier discharge (DBD) microplasma as a radiation source for optical emission spectrometry (OES) is extended by nickel carbonyl vapor generation. We proved that metal carbonyl completely avoids the extinguishing of plasma, and it is much more suitable for matching the DBD excitation and OES detection with respect to significant DBD quenching by concomitant hydrogen when hydride generation is used. A concentric quartz UV reactor allows sample solution to flow through the central channel wherein to efficiently receive the uniformly distributed UV irradiation in the confined cylindrical space between the concentric tubes, which facilitates effective carbonyl generation in a nickel solution. The carbonyl is transferred into the DBD excitation chamber by an argon stream for nickel excitation, and the characteristic emission of nickel at 232.0 nm is detected by a charge-coupled device (CCD) spectrometer. A 1.0 mL sample solution results in a linear range of 5-100 μg L(-1) along with a detection limit of 1.3 μg L(-1) and a precision of 2.4% RSD at 50 μg L(-1). The present DBD-OES system is validated by nickel in certified reference materials.

  11. Metal complexes of quinolone antibiotics and their applications: an update.

    PubMed

    Uivarosi, Valentina

    2013-09-11

    Quinolones are synthetic broad-spectrum antibiotics with good oral absorption and excellent bioavailability. Due to the chemical functions found on their nucleus (a carboxylic acid function at the 3-position, and in most cases a basic piperazinyl ring (or another N-heterocycle) at the 7-position, and a carbonyl oxygen atom at the 4-position) quinolones bind metal ions forming complexes in which they can act as bidentate, as unidentate and as bridging ligand, respectively. In the polymeric complexes in solid state, multiple modes of coordination are simultaneously possible. In strongly acidic conditions, quinolone molecules possessing a basic side nucleus are protonated and appear as cations in the ionic complexes. Interaction with metal ions has some important consequences for the solubility, pharmacokinetics and bioavailability of quinolones, and is also involved in the mechanism of action of these bactericidal agents. Many metal complexes with equal or enhanced antimicrobial activity compared to the parent quinolones were obtained. New strategies in the design of metal complexes of quinolones have led to compounds with anticancer activity. Analytical applications of complexation with metal ions were oriented toward two main directions: determination of quinolones based on complexation with metal ions or, reversely, determination of metal ions based on complexation with quinolones.

  12. Aryl-palladium-NHC complex: efficient phosphine-free catalyst precursors for the carbonylation of aryl iodides with amines or alkynes.

    PubMed

    Zhang, Chunyan; Liu, Jianhua; Xia, Chungu

    2014-12-21

    A series of aryl-palladium-NHC compounds was prepared according to the reported methods and their catalytic activity in the carbonylation of aryl iodides to synthesize α-keto amides and alkynones was examined. These practical aryl-palladium-NHC complexes have shown highly efficient catalyzed carbonylation and Sonogashira carbonylation reactions, with high turnover number in synthesis of α-keto amides (TON = 4300) and in synthesis of alkynones (TON = 980).

  13. COATING URANIUM FROM CARBONYLS

    DOEpatents

    Gurinsky, D.H.; Storrs, S.S.

    1959-07-14

    Methods are described for making adherent corrosion resistant coatings on uranium metal. According to the invention, the uranium metal is heated in the presence of an organometallic compound such as the carbonyls of nickel, molybdenum, chromium, niobium, and tungsten at a temperature sufficient to decompose the metal carbonyl and dry plate the resultant free metal on the surface of the uranium metal body. The metal coated body is then further heated at a higher temperature to thermally diffuse the coating metal within the uranium bcdy.

  14. Polynuclear Gold [AuI]4, [AuI]8, and Bimetallic [AuI 4AgI] Complexes: C−H Functionalization of Carbonyl Compounds and Homogeneous Carbonylation of Amines

    PubMed Central

    Smirnova, Ekaterina S.; Muñoz Molina, José M.; Johnson, Alice; Bandeira, Nuno A. G.; Bo, Carles

    2016-01-01

    Abstract The synthesis of tetranuclear gold complexes, a structurally unprecedented octanuclear complex with a planar [AuI 8] core, and pentanuclear [AuI 4MI] (M=Cu, Ag) complexes is presented. The linear [AuI 4] complex undergoes C−H functionalization of carbonyl compounds under mild reaction conditions. In addition, [AuI 4AgI] catalyzes the carbonylation of primary amines to form ureas under homogeneous conditions with efficiencies higher than those achieved by gold nanoparticles. PMID:27167611

  15. [Defects in TOR regulatory complexes retard aging and carbonyl/oxidative stress development in yeast Saccharomyces cerevisiae].

    PubMed

    Homza, B V; Vasyl'kovs'ka, R A; Semchyshyn, H M

    2014-01-01

    TOR signaling pathway first described in yeast S. cerevisiae is the highly conserved regulator of eukaryotic cell growth, aging and stress resistance. The effect of nitrogen sources, in particular amino acids, on the activity of TOR signaling pathway is well studied, however its relation to carbohydrates is poor understood. The aim of the present study is expanding of our understanding of potential role of TOR regulatory complexes in development of carbonyl/oxidative stress that can result from yeast cultivation on glucose and fructose. It has been shown that the level of alpha-dicarbonyl compounds and protein carbonyl groups increased with time of yeast cultivation and was higher in cells grown on fructose that demonstrated their accelerated aging and carbonyl/oxidative stress development as compared with cells grown on glucose. The strains defective in TOR proteins cultivated in the presence of glucose as well as fructose demonstrated lower markers of the stress and aging than parental strain. Thus these data confirmed the previous conclusion on fructose more potent ability to cause carbonyl/oxidative stress and accelerated aging in S. cerevisiae as compared with glucose. However, defects in TOR regulatory complexes retard aging and development of the stress in yeast independent on the type of carbohydrate in the cultivation medium.

  16. A simple, general route to 2-pyridylidene transition metal complexes.

    PubMed

    Roselló-Merino, Marta; Díez, Josefina; Conejero, Salvador

    2010-12-28

    Pyridinium 2-carboxylates decompose thermally in the presence of a variety of late transition metal precursors to yield the corresponding 2-pyridylidene-like complexes. The mild reaction conditions and structural diversity that can be generated in the heterocyclic ring make this method an attractive alternative for the synthesis of 2-pyridylidene complexes. IR spectra of the Ir(i) carbonyl compounds [IrCl(NHC)(CO)(2)] indicate that these N-heterocyclic carbene ligands are among the strongest σ-electron donors.

  17. The synthesis of PNP-supported low-spin nitro manganese(I) carbonyl complexes

    DOE PAGES

    Tondreau, Aaron M.; Boncella, James M.

    2016-09-01

    In this study, the coordination chemistry of Mn(CO)5Br was investigated with a series of PNP-pincer ligands. The ligands iPrPONOP (iPrPONOP = 2,6-bis(diisopropylphosphinito)pyridine) and iPrPNHP (iPrPNHP = HN{CH2CH2(PiPr2)}2) gave the desired organometallic manganese complexes (iPrPONOP)Mn(CO)2Br and (iPrPNHP)Mn(CO)2Br, respectively, upon chelation to Mn(CO)5Br. The reactivity of iPrPNNNP (iPrPNNNP = N,N'-bis(diisopropylphosphino)-2,6-diaminopyridine) with Mn(CO)5Br yielded a pair of products, [(iPrPNNNP)Mn(CO)3][Br] and (iPrPNNNCO)Mn(CO)3. The formation of the asymmetric chelate arises from a formal loss of iPr2PBr and C–N bond formation from a carbonyl ligand and NH, yielding a Mn(I) amide core. The nitration reactions of (iPrPONOP)Mn(CO)2Br and (iPrPNHP)Mn(CO)2Br were carried out using silver nitrite, yieldingmore » the nitro compounds (iPrPONOP)Mn(CO)2(NO2) and (iPrPNHP)Mn(CO)2(NO2), respectively. The analogous iron complex (iPrPONOP)Fe(CO)Cl2 was nitrated under the same conditions to yield the salt pair [(iPrPONOP)Fe(CO)2][FeCl3NO]. This reactivity underlines the difference between iso-valent iron and manganese centers. The manganese complexes (iPrPONOP)Mn(CO)2(NO2) and (iPrPNHP)Mn(CO)2(NO2) were ineffective as oxygen atom transfer reagents for a variety of substrates.« less

  18. Tungsten carbonyl σ-complexes with charge-compensated nido-carboranyl thioether ligands.

    PubMed

    Timofeev, Sergey V; Zhidkova, Olga B; Mosolova, Elena M; Sivaev, Igor B; Godovikov, Ivan A; Suponitsky, Kyrill Yu; Starikova, Zoya A; Bregadze, Vladimir I

    2015-04-14

    Charge-compensated nido-carboranyl thioether ligands [7-MeS-10-Me2S-7,8-C2B9H10] and [7,8-(MeS)2-10-Me2S-7,8-C2B9H9] were prepared and fully characterized. They readily react with labile tungsten carbonyls to give σ-complexes - mono-substituted (CO)5W[7-MeS-10-Me2S-7,8-C2B9H10-κ(1)-S(1)] and (CO)5W[7,8-(MeS)2-10-Me2S-7,8-C2B9H9-κ(1)-S(1)] and chelate (CO)4W[7,8-(MeS)2-10-Me2S-7,8-C2B9H9-κ(2)-S(1),S(2)]. The synthesized metallocomplexes were characterized by multinuclear NMR spectroscopy and single crystal X-ray diffraction. The donor ability of the 7-methylsulfide-nido-carborane ligand is not sensitive to introduction of the charge-compensating dimethylsulfonium group.

  19. Catalysis of the carbonylation of olefins by the cationic chromium complexes allyl(arene)dicarbonylchromium(I) tetrafluoroborates

    SciTech Connect

    Magomedov, G.K.I.; Morozova, L.V.; Sigachev, S.A.; Krivykh, V.V.; Taits, E.S.; Rybinskaya, M.I.

    1986-11-10

    A qualitative comparison of the catalytic activities of the title complexes and cobalt carbonyl showed that (arene)allyldicarbonylchromium(I) tetrafluoroborates are more active than cobalt carbonyl, and this applies particularly to (C/sub 6/H/sub 6/Cr(CO)/sub 2/..pi..-C/sub 3/H/sub 5/)/sup +/BF/sub 4/. The possibility is not ruled out that in the course of the synthesis the acid HBF/sub 4/ is generated, and this is known to be a catalyst for the Koch reaction, but in this reaction only secondary and tertiary carboxy derivatives, i.e., only products of addition in accordance with the Markovnikov rule, are formed. In view of these results the authors investigated the activity of the title complexes in the hydroformylation process, an important industrial method for the preparation of aldehydes and alcohols.

  20. Reactivity of surface carbonyl complexes in NO reduction with CO on copper-containing high-silica zeolites

    SciTech Connect

    Ukharskii, A.A.; Il`ichev, A.N.; Matyshak, V.A.

    1995-09-01

    Two mechanisms of NO reduction with CO were revealed on copper-containing high-silica zeolites. The low-temperature mechanism (below 300{degrees}C) involves the interaction between NO and CO adsorbed on Cu{sup +} with the formation of N{sub 2}0 and CO{sub 2}. The high-temperature mechanism (above 300{degrees}C) includes the interaction of CO molecules, adsorbed on Cu{sup +} ions, with NO molecules, adsorbed on copper atoms, with the formation of N{sub 2} and CO{sub 2}. Under reaction conditions, a surface carbonyl complex, CO-Cu{sup +} is observed. Quantitative spectrokinetic data provide evidence for the intermediacy of the carbonyl complex in both mechanisms. A correlation between the activity in the reaction of NO reduction with CO and the amount of Cu{sup O} atoms in the sample is found.

  1. Metal-catalyzed reductive coupling of olefin-derived nucleophiles: Reinventing carbonyl addition.

    PubMed

    Nguyen, Khoa D; Park, Boyoung Y; Luong, Tom; Sato, Hiroki; Garza, Victoria J; Krische, Michael J

    2016-10-21

    α-Olefins are the most abundant petrochemical feedstock beyond alkanes, yet their use in commodity chemical manufacture is largely focused on polymerization and hydroformylation. The development of byproduct-free catalytic C-C bond-forming reactions that convert olefins to value-added products remains an important objective. Here, we review catalytic intermolecular reductive couplings of unactivated and activated olefin-derived nucleophiles with carbonyl partners. These processes represent an alternative to the longstanding use of stoichiometric organometallic reagents in carbonyl addition. Copyright © 2016, American Association for the Advancement of Science.

  2. The synthesis of PNP-supported low-spin nitro manganese(I) carbonyl complexes

    SciTech Connect

    Tondreau, Aaron M.; Boncella, James M.

    2016-09-01

    In this study, the coordination chemistry of Mn(CO)5Br was investigated with a series of PNP-pincer ligands. The ligands iPrPONOP (iPrPONOP = 2,6-bis(diisopropylphosphinito)pyridine) and iPrPNHP (iPrPNHP = HN{CH2CH2(PiPr2)}2) gave the desired organometallic manganese complexes (iPrPONOP)Mn(CO)2Br and (iPrPNHP)Mn(CO)2Br, respectively, upon chelation to Mn(CO)5Br. The reactivity of iPrPNNNP (iPrPNNNP = N,N'-bis(diisopropylphosphino)-2,6-diaminopyridine) with Mn(CO)5Br yielded a pair of products, [(iPrPNNNP)Mn(CO)3][Br] and (iPrPNNNCO)Mn(CO)3. The formation of the asymmetric chelate arises from a formal loss of iPr2PBr and C–N bond formation from a carbonyl ligand and NH, yielding a Mn(I) amide core. The nitration reactions of (iPrPONOP)Mn(CO)2Br and (iPrPNHP)Mn(CO)2Br were carried out using silver nitrite, yielding the nitro compounds (iPrPONOP)Mn(CO)2(NO2) and (iPrPNHP)Mn(CO)2(NO2), respectively. The analogous iron complex (iPrPONOP)Fe(CO)Cl2 was nitrated under the same conditions to yield the salt pair [(iPrPONOP)Fe(CO)2][FeCl3NO]. This reactivity underlines the difference between iso-valent iron and manganese centers. The manganese complexes (iPrPONOP)Mn(CO)2(NO2) and (iPrPNHP)Mn(CO)2(NO2) were ineffective as oxygen atom transfer reagents for a variety of substrates.

  3. The synthesis of PNP-supported low-spin nitro manganese(I) carbonyl complexes

    SciTech Connect

    Tondreau, Aaron M.; Boncella, James M.

    2016-09-01

    In this study, the coordination chemistry of Mn(CO)5Br was investigated with a series of PNP-pincer ligands. The ligands iPrPONOP (iPrPONOP = 2,6-bis(diisopropylphosphinito)pyridine) and iPrPNHP (iPrPNHP = HN{CH2CH2(PiPr2)}2) gave the desired organometallic manganese complexes (iPrPONOP)Mn(CO)2Br and (iPrPNHP)Mn(CO)2Br, respectively, upon chelation to Mn(CO)5Br. The reactivity of iPrPNNNP (iPrPNNNP = N,N'-bis(diisopropylphosphino)-2,6-diaminopyridine) with Mn(CO)5Br yielded a pair of products, [(iPrPNNNP)Mn(CO)3][Br] and (iPrPNNNCO)Mn(CO)3. The formation of the asymmetric chelate arises from a formal loss of iPr2PBr and C–N bond formation from a carbonyl ligand and NH, yielding a Mn(I) amide core. The nitration reactions of (iPrPONOP)Mn(CO)2Br and (iPrPNHP)Mn(CO)2Br were carried out using silver nitrite, yielding the nitro compounds (iPrPONOP)Mn(CO)2(NO2) and (iPrPNHP)Mn(CO)2(NO2), respectively. The analogous iron complex (iPrPONOP)Fe(CO)Cl2 was nitrated under the same conditions to yield the salt pair [(iPrPONOP)Fe(CO)2][FeCl3NO]. This reactivity underlines the difference between iso-valent iron and manganese centers. The manganese complexes (iPrPONOP)Mn(CO)2(NO2) and (iPrPNHP)Mn(CO)2(NO2) were ineffective as oxygen atom transfer reagents for a variety of substrates.

  4. Photolithographic Encoding of Metal Complexes.

    PubMed

    Lang, Christiane; Bestgen, Sebastian; Welle, Alexander; Müller, Rouven; Roesky, Peter W; Barner-Kowollik, Christopher

    2015-10-12

    A platform technology for the creation of spatially resolved surfaces encoded with a monolayer consisting of different metal complexes was developed. The concept entails the light-triggered activation of a self- assembled monolayer (SAM) of UV-labile anchors, that is, phenacylsulfides, and the subsequent cycloaddition of selected diene-functionalized metal complexes at defined areas on the surface. The synthesis and characterization of the metal complexes for the UV-light assisted anchoring on the surface and a detailed study of a short-chain oligomer model system in solution confirm the high efficiency of the photoreaction. The hybrid materials obtained by this concept can potentially be utilized for the design of highly valuable catalytic or (opto-)electronic devices. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Two-Electron Carbon Dioxide Reduction Catalyzed by Rhenium(I) Bis(imino)acenaphthene Carbonyl Complexes

    PubMed Central

    Portenkirchner, Engelbert; Kianfar, Elham; Sariciftci, Niyazi Serdar; Knör, Günther

    2014-01-01

    Rhenium(I) carbonyl complexes carrying substituted bis(arylimino)acenaphthene ligands (BIAN-R) have been tested as potential catalysts for the two-electron reduction of carbon dioxide. Cyclic voltammetric studies as well as controlled potential electrolysis experiments were performed using CO2-saturated solutions of the complexes in acetonitrile and acetonitrile–water mixtures. Faradaic efficiencies of more than 30 % have been determined for the electrocatalytic production of CO. The effects of ligand substitution patterns and water content of the reaction medium on the catalytic performance of the new catalysts are discussed. PMID:24737649

  6. Trifluorosulfane ligand as an analogue of the nitrosyl ligand: highly exothermic fluorine transfer reactions from sulfur to metal in the chemistry of SF3 metal carbonyls of the first row transition metals.

    PubMed

    Deng, Jianming; Wang, Chaoyang; Li, Qian-shu; Xie, Yaoming; King, R Bruce; Schaefer, Henry F

    2011-04-04

    The variety of known very stable PF(3) metal derivatives analogous to metal carbonyls suggests the synthesis of SF(3) metal derivatives analogous to metal nitrosyls. However, the only known SF(3) metal complex is the structurally uncharacterized (Et(3)P)(2)Ir(CO)(Cl)(F)(SF(3)) synthesized by Cockman, Ebsworth, and Holloway in 1987 and suggested by electron counting to have a one-electron donor SF(3) group rather than a three-electron donor SF(3) group. In this connection, the possibility of synthesizing SF(3) metal derivatives analogous to metal nitrosyls has been investigated using density functional theory. The [M]SF(3) derivatives with [M] = V(CO)(5), Mn(CO)(4), Co(CO)(3), Ir(CO)(3), (C(5)H(5))Cr(CO)(2), (C(5)H(5))Fe(CO), and (C(5)H(5))Ni analogous to known metal nitrosyl derivatives are all predicted to be thermodynamically disfavored with respect to the corresponding [M](SF(2))(F) derivatives by energies ranging from 19.5 kcal/mol for Mn(SF(3))(CO)(4) to 5.4 kcal/mol for Co(SF(3))(CO)(3). By contrast, the isoelectronic [M]PF(3) derivatives with [M] = Cr(CO)(5), Fe(CO)(4), Ni(CO)(3), (C(5)H(5))Mn(CO)(2), (C(5)H(5))Co(CO), and (C(5)H(5))Cu are all very strongly thermodynamically favored with respect to the corresponding [M](PF(2))(F) derivatives by energies ranging from 64.3 kcal/mol for Cr(PF(3))(CO)(5) to 31.6 kcal/mol for (C(5)H(5))Co(PF(3))(CO). The known six-coordinate (Et(3)P)(2)Ir(CO)(Cl)(F)(SF(3)) is also predicted to be stable relative to the seven-coordinate (Et(3)P)(2)Ir(CO)(Cl)(F)(2)(SF(2)). Most of the metal SF(3) complexes found in this work are singlet structures containing three-electron donor SF(3) ligands with tetrahedral sulfur coordination. However, two examples of triplet spin state metal SF(3) complexes, namely, the lowest energy (C(5)H(5))Fe(SF(3))(CO) structure and a higher energy Co(SF(3))(CO)(3) structure, are found containing one-electron donor SF(3) ligands with pseudo square pyramidal sulfur coordination with a stereochemically

  7. Solid-state thermolysis of a fac-rhenium(I) carbonyl complex with a redox non-innocent pincer ligand.

    PubMed

    Jurca, Titel; Chen, Wen-Ching; Michel, Sheila; Korobkov, Ilia; Ong, Tiow-Gan; Richeson, Darrin S

    2013-03-25

    The development of rhenium(I) chemistry has been restricted by the limited structural and electronic variability of the common pseudo-octahedral products fac-[ReX(CO)3L2] (L2 = α-diimine). We address this constraint by first preparing the bidentate bis(imino)pyridine complexes [(2,6-{2,6-Me2C6H3N=CPh}2C5H3N)Re(CO)3X] (X = Cl 2, Br 3), which were characterized by spectroscopic and X-ray crystallographic means, and then converting these species into tridentate pincer ligand compounds, [(2,6-{2,6-Me2C6H3N=CPh}2C5H3N)Re(CO)2X] (X = Cl 4, Br 5). This transformation was performed in the solid-state by controlled heating of 2 or 3 above 200 °C in a tube furnace under a flow of nitrogen gas, giving excellent yields (≥95 %). Compounds 4 and 5 define a new coordination environment for rhenium(I) carbonyl chemistry where the metal center is supported by a planar, tridentate pincer-coordinated bis(imino)pyridine ligand. The basic photophysical features of these compounds show significant elaboration in both number and intensity of the d-π* transitions observed in the UV/Vis spec tra relative to the bidentate starting materials, and these spectra were analyzed using time-dependent DFT computations. The redox nature of the bis(imino)pyridine ligand in compounds 2 and 4 was examined by electrochemical analysis, which showed two ligand reduction events and demonstrated that the ligand reduction shifts to a more positive potential when going from bidentate 2 to tridentate 4 (+160 mV for the first reduction step and +90 mV for the second). These observations indicate an increase in electrostatic stabilization of the reduced ligand in the tridentate conformation. Elaboration on this synthetic methodology documented its generality through the preparation of the pseudo-octahedral rhenium(I) triflate complex [(2,6-{2,6-Me2C6H3N=CPh}2C5H3N)Re(CO)2OTf] (7, 93 % yield). Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Electrocatalytic reduction of carbon dioxide with Mn(terpyridine) carbonyl complexes.

    PubMed

    Machan, Charles W; Kubiak, Clifford P

    2016-11-01

    The behavior of a series of Manganese (Mn) carbonyl compounds with 2,2':6',2''-terpyridine (tpy) in κ(2)-N,N' and κ(3)-N,N',N'' coordination modes under electrochemically reducing conditions is reported. In the presence of carbon dioxide (CO2) and Brønsted acid (phenol), two-electron reduction to carbon monoxide (CO) and water (H2O) is observed. Based on data obtained from cyclic voltammetry and infrared spectroelectrochemistry, the active state of the catalyst in the proposed mechanism for all cases is [Mn(κ(3)-N,N',N''-tpy)(CO)2](-). Under these conditions, competing decomposition reactions limit the overall Faradaic efficiency. These results suggest the possibility of developing new tridentate ligand frameworks suitable for catalytic systems with Mn carbonyl cores.

  9. Pressure-induced Transformations of Dense Carbonyl Sulfide to Singly Bonded Amorphous Metallic Solid

    NASA Astrophysics Data System (ADS)

    Kim, Minseob; Dias, Ranga; Ohishi, Yasuo; Matsuoka, Takehiro; Chen, Jing-Yin; Yoo, Choong-Shik

    2016-08-01

    The application of pressure, internal or external, transforms molecular solids into non-molecular extended network solids with diverse crystal structures and electronic properties. These transformations can be understood in terms of pressure-induced electron delocalization; however, the governing mechanisms are complex because of strong lattice strains, phase metastability and path dependent phase behaviors. Here, we present the pressure-induced transformations of linear OCS (R3m, Phase I) to bent OCS (Cm, Phase II) at 9 GPa an amorphous, one-dimensional (1D) polymer at 20 GPa (Phase III); and an extended 3D network above ~35 GPa (Phase IV) that metallizes at ~105 GPa. These results underscore the significance of long-range dipole interactions in dense OCS, leading to an extended molecular alloy that can be considered a chemical intermediate of its two end members, CO2 and CS2.

  10. Pressure-induced Transformations of Dense Carbonyl Sulfide to Singly Bonded Amorphous Metallic Solid

    PubMed Central

    Kim, Minseob; Dias, Ranga; Ohishi, Yasuo; Matsuoka, Takehiro; Chen, Jing-Yin; Yoo, Choong-Shik

    2016-01-01

    The application of pressure, internal or external, transforms molecular solids into non-molecular extended network solids with diverse crystal structures and electronic properties. These transformations can be understood in terms of pressure-induced electron delocalization; however, the governing mechanisms are complex because of strong lattice strains, phase metastability and path dependent phase behaviors. Here, we present the pressure-induced transformations of linear OCS (R3m, Phase I) to bent OCS (Cm, Phase II) at 9 GPa; an amorphous, one-dimensional (1D) polymer at 20 GPa (Phase III); and an extended 3D network above ~35 GPa (Phase IV) that metallizes at ~105 GPa. These results underscore the significance of long-range dipole interactions in dense OCS, leading to an extended molecular alloy that can be considered a chemical intermediate of its two end members, CO2 and CS2. PMID:27527241

  11. Ruthenium(II) carbonyl complexes containing pyridine carboxamide ligands and PPh3/AsPh3/Py coligands: Synthesis, spectral characterization, catalytic and antioxidant studies

    NASA Astrophysics Data System (ADS)

    Ramachandran, Rangasamy; Viswanathamurthi, Periasamy

    2013-02-01

    New ruthenium(II) carbonyl complexes bearing pyridine carboxamide and triphenylphosphine/triphenylarsine/pyridine have been prepared by direct reaction of ruthenium(II) precursors with some pyridine carboxamide ligands, N,N-bis(2-pyridinecarboxamide)-1,2-ethane (H2L1), N,N-bis(2-pyridinecarboxamide)-1,2-benzene (H2L2) and N,N-bis(2-pyridinecarboxamide)-trans-1,2-cyclohexane (H2L3). The organic ligands offering two Namide and two Npyridine donor sites to the metal centre. They have been characterized by elemental analyses, FT-IR, UV-Visible, NMR (1H, 13C and 31P) and ESI-MS techniques. Based on the above data, an octahedral structure has been assigned for all the complexes. The catalytic efficiency of the complexes in transfer hydrogenation of ketones in the presence of iPrOH/KOH and N-alkylation of amine in the presence of tBuOK was examined. Furthermore, the antioxidant activity of the ligands and its ruthenium(II) complexes were determined by DPPH radical, nitric oxide radical, hydroxyl radical and hydrogen peroxide scavenging methods, which indicates that the ruthenium(II) complexes exhibit more effective antioxidant activity than the ligands alone.

  12. Formazans and their metal complexes

    NASA Astrophysics Data System (ADS)

    Sigeikin, Gennadii I.; Lipunova, Galina N.; Pervova, I. G.

    2006-10-01

    The current data on the structure of formazans in crystals and in solutions are considered and some problems of tautomeric and conformational equilibria are discussed. Some novel classes of formazans synthesised over the past decade are presented. The results of structural studies of formazan complexes with various types of metal coordination are generalised. Examples of synthesis of formazan-containing polymers are given. Special emphasis is placed on analytical and practical applications of formazan derivatives.

  13. Metal carbonyl-hydrosilane reactions and hydrosilation catalysis. Final report for period May 1, 1995 - August 14, 1999

    SciTech Connect

    Cutler, Alan R.

    2001-04-14

    Manganese carbonyl complexes serve as hydrosilation precatalysts for selectively transforming a carbonyl group into a doxy methylene or a fully reduced methylene group. Substrates of interest include (1) aldehydes, ketones, carboxylic acids, silyl esters, and esters, and (2) their organometallic acyl counterparts. Two types of manganese precatalysts have been reported: (a) alkyl and acyl complexes (L)(CO){sub 4}MnR [L = CO, PPh{sub 3}; R = COCH{sub 3}, COPh, CH{sub 3}] and (b) halides (CO){sub 5}MnX and [(CO){sub 4}MnX]{sub 2} (X = Br, I). The former promote hydrosilation and deoxygenation catalysis; the latter promote dehydrogenative silation of alcohols and carboxylic acids as well as hydrosilation and deoxygenation of some metallocarboxylic acid derivatives. In every case studied, these Mn precatalysts are far more reactive or selective than traditional Rh(l) precatalysts. The reaction chemistry of the above and other Mn alkyl complexes with hydrosilanes was studied in order to probe catalysis mechanism(s). Thus, Mn(CO){sub 5} methyl, benzyl, acetyl, and benzoyl (4 p-substituents) complexes reacted with hydrosilines by four different mechanisms, which were established. A noteworthy development was that the methyl and benzoyl complexes gave moderate yields of a new ({eta}{sup 2}-Si-H) silane adduct (CO){sub 4}Mn(SiMe{sub 2}Ph)(H-SiMe{sub 2}Ph), which is stable in the presence of excess silane. This silane adduct promotes all three catalytic reactions; its extraordinary activity and potential selectivity are under study.

  14. Separation and Identification of a Mixture of Group 6 Transition-Metal Carbonyl Compounds Using GC-MS in the General Chemistry Curriculum

    ERIC Educational Resources Information Center

    Fong, Lawrence K.

    2004-01-01

    Students in the general chemistry course are advised to scrutinize data obtained by gas chromatograph (GC) for segregation, and mass spectroscopy (MS) for recognizing combination of group 6 transition-metal carbonyl compounds. The GC-MS method arouses students' interest, as it can be applied to real-world situations, such as the routine…

  15. Separation and Identification of a Mixture of Group 6 Transition-Metal Carbonyl Compounds Using GC-MS in the General Chemistry Curriculum

    ERIC Educational Resources Information Center

    Fong, Lawrence K.

    2004-01-01

    Students in the general chemistry course are advised to scrutinize data obtained by gas chromatograph (GC) for segregation, and mass spectroscopy (MS) for recognizing combination of group 6 transition-metal carbonyl compounds. The GC-MS method arouses students' interest, as it can be applied to real-world situations, such as the routine…

  16. Carbonyl Activation by Borane Lewis Acid Complexation: Transition States of H2 Splitting at the Activated Carbonyl Carbon Atom in a Lewis Basic Solvent and the Proton-Transfer Dynamics of the Boroalkoxide Intermediate.

    PubMed

    Heshmat, Mojgan; Privalov, Timofei

    2017-07-06

    By using transition-state (TS) calculations, we examined how Lewis acid (LA) complexation activates carbonyl compounds in the context of hydrogenation of carbonyl compounds by H2 in Lewis basic (ethereal) solvents containing borane LAs of the type (C6 F5 )3 B. According to our calculations, LA complexation does not activate a ketone sufficiently enough for the direct addition of H2 to the O=C unsaturated bond; but, calculations indicate a possibly facile heterolytic cleavage of H2 at the activated and thus sufficiently Lewis acidic carbonyl carbon atom with the assistance of the Lewis basic solvent (i.e., 1,4-dioxane or THF). For the solvent-assisted H2 splitting at the carbonyl carbon atom of (C6 F5 )3 B adducts with different ketones, a number of TSs are computed and the obtained results are related to insights from experiment. By using the Born-Oppenheimer molecular dynamics with the DFT for electronic structure calculations, the evolution of the (C6 F5 )3 B-alkoxide ionic intermediate and the proton transfer to the alkoxide oxygen atom were investigated. The results indicate a plausible hydrogenation mechanism with a LA, that is, (C6 F5 )3 B, as a catalyst, namely, 1) the step of H2 cleavage that involves a Lewis basic solvent molecule plus the carbonyl carbon atom of thermodynamically stable and experimentally identifiable (C6 F5 )3 B-ketone adducts in which (C6 F5 )3 B is the "Lewis acid promoter", 2) the transfer of the solvent-bound proton to the oxygen atom of the (C6 F5 )3 B-alkoxide intermediate giving the (C6 F5 )3 B-alcohol adduct, and 3) the SN 2-style displacement of the alcohol by a ketone or a Lewis basic solvent molecule. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Two-electron carbon dioxide reduction catalyzed by rhenium(I) bis(imino)acenaphthene carbonyl complexes.

    PubMed

    Portenkirchner, Engelbert; Kianfar, Elham; Sariciftci, Niyazi Serdar; Knör, Günther

    2014-05-01

    Rhenium(I) carbonyl complexes carrying substituted bis(arylimino)acenaphthene ligands (BIAN-R) have been tested as potential catalysts for the two-electron reduction of carbon dioxide. Cyclic voltammetric studies as well as controlled potential electrolysis experiments were performed using CO2-saturated solutions of the complexes in acetonitrile and acetonitrile-water mixtures. Faradaic efficiencies of more than 30 % have been determined for the electrocatalytic production of CO. The effects of ligand substitution patterns and water content of the reaction medium on the catalytic performance of the new catalysts are discussed. © 2014 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.

  18. Exploring the Cellular Accumulation of Metal Complexes

    PubMed Central

    Puckett, Cindy A.; Ernst, Russell J.; Barton, Jacqueline K.

    2010-01-01

    Transition metal complexes offer great potential as diagnostic and therapeutic agents, and a growing number of biological applications have been explored. To be effective, these complexes must reach their intended target inside the cell. Here we review the cellular accumulation of metal complexes, including their uptake, localization, and efflux. Metal complexes are taken up inside cells through various mechanisms, including passive diffusion and entry through organic and metal transporters. Emphasis is placed on the methods used to examine cellular accumulation, to identify the mechanism(s) of uptake, and to monitor possible efflux. Conjugation strategies that have been employed to improve the cellular uptake characteristics of metal complexes are also described. PMID:20104335

  19. Highly efficient energy transfer from a carbonyl carotenoid to chlorophyll a in the main light harvesting complex of Chromera velia.

    PubMed

    Durchan, Milan; Keşan, Gürkan; Slouf, Václav; Fuciman, Marcel; Staleva, Hristina; Tichý, Josef; Litvín, Radek; Bína, David; Vácha, František; Polívka, Tomáš

    2014-10-01

    We report on energy transfer pathways in the main light-harvesting complex of photosynthetic relative of apicomplexan parasites, Chromera velia. This complex, denoted CLH, belongs to the family of FCP proteins and contains chlorophyll (Chl) a, violaxanthin, and the so far unidentified carbonyl carotenoid related to isofucoxanthin. The overall carotenoid-to-Chl-a energy transfer exhibits efficiency over 90% which is the largest among the FCP-like proteins studied so far. Three spectroscopically different isofucoxanthin-like molecules were identified in CLH, each having slightly different energy transfer efficiency that increases from isofucoxanthin-like molecules absorbing in the blue part of the spectrum to those absorbing in the reddest part of spectrum. Part of the energy transfer from carotenoids proceeds via the ultrafast S2 channel of both the violaxanthin and isofucoxanthin-like carotenoid, but major energy transfer pathway proceeds via the S1/ICT state of the isofucoxanthin-like carotenoid. Two S1/ICT-mediated channels characterized by time constants of ~0.5 and ~4ps were found. For the isofucoxanthin-like carotenoid excited at 480nm the slower channel dominates, while those excited at 540nm employs predominantly the fast 0.5ps channel. Comparing these data with the excited-state properties of the isofucoxanthin-like carotenoid in solution we conclude that, contrary to other members of the FCP family employing carbonyl carotenoids, CLH complex suppresses the charge transfer character of the S1/ICT state of the isofucoxanthin-like carotenoid to achieve the high carotenoid-to-Chl-a energy transfer efficiency.

  20. Complex formation between the uncoupler carbonyl cyanide p-trifluoromethoxyphenylhydrazone (FCCP) and valinomycin in the presence of potassium.

    PubMed

    O'Brien, T A; Nieva-Gomez, D; Gennis, R B

    1978-03-25

    Spectroscopic evidence is presented which indicates that the uncoupler carbonyl cyanide p-trifluoromethoxyphenylhydrazone (FCCP) and the peptide antibiotic valinomycin form a complex in the presence of potassium. Complex formation has been observed both in aqueous and nonaqueous media. Several techniques have been used to indicate the existence of a complex in aqueous solution. In the presence of valinomycin and K+, the absorption spectrum of FCCP is significantly perturbed, and there is also a large induced circular dichroism signal. In addition, the previously characterized complex which forms between valinomycin, K+, and the fluorescent probe 8-anilino-1-naphthalene-sulfonate (ANS) in aqueous solution is apparently disrupted by the addition of FCCP. The result is an effective quenching of the fluorescence due to the bound probe as it is displaced from the valinomycin.K+ by the uncoupler. In a nonpolar solvent, the absorption spectrum of FCCP is also perturbed by valinomycin in the presence of K+, again indicating the formation of a complex. These data point to the importance of considering the role of valinomycin.K+.uncoupler complex in interpreting physiological or ion transport data in which these substances have been used together.

  1. Synthesis and structures of photoactive manganese-carbonyl complexes derived from 2-(pyridin-2-yl)-1,3-benzothiazole and 2-(quinolin-2-yl)-1,3-benzothiazole.

    PubMed

    Stenger-Smith, Jenny; Chakraborty, Indranil; Carrington, Samantha; Mascharak, Pradip

    2017-04-01

    PhotoCORMs (photo-active CO-releasing molecules) have emerged as a class of CO donors where the CO release process can be triggered upon illumination with light of appropriate wavelength. We have recently reported an Mn-based photoCORM, namely [MnBr(pbt)(CO)3] [pbt is 2-(pyridin-2-yl)-1,3-benzothiazole], where the CO release event can be tracked within cellular milieu by virtue of the emergence of strong blue fluorescence. In pursuit of developing more such trackable photoCORMs, we report herein the syntheses and structural characterization of two Mn(I)-carbonyl complexes, namely fac-tricarbonylchlorido[2-(pyridin-2-yl)-1,3-benzothiazole-κ(2)N,N']manganese(I), [MnCl(C12H8N2S)(CO)3], (1), and fac-tricarbonylchlorido[2-(quinolin-2-yl)-1,3-benzothiazole-κ(2)N,N']manganese(I), [MnCl(C16H10N2S)(CO)3], (2). In both complexes, the Mn(I) center resides in a distorted octahedral coordination environment. Weak intermolecular C-H...Cl contacts in complex (1) and Cl...S contacts in complex (2) consolidate their extended structures. These complexes also exhibit CO release upon exposure to low-power broadband visible light. The apparent CO release rates for the two complexes have been measured to compare their CO donating capacity. The fluorogenic 2-(pyridin-2-yl)-1,3-benzothiazole and 2-(quinolin-2-yl)-1,3-benzothiazole ligands provide a convenient way to track the CO release event through the `turn-ON' fluorescence which results upon de-ligation of the ligands from their respective metal centers following CO photorelease.

  2. Synthesis, characterization, and gas-phase fragmentation of rhenium-carbonyl complexes bearing imidazol(in)ium-2-dithiocarboxylate ligands.

    PubMed

    Beltrán, Tomás F; Zaragoza, Guillermo; Delaude, Lionel

    2016-11-15

    Five complexes with the generic formula [ReBr(CO)3(κ(2)-S,S'-S2C·NHC)] were obtained by reacting [ReBr(CO)5] with a set of representative imidazol(in)ium-2-dithiocarboxylate zwitterions. These ligands are the adducts of N-heterocyclic carbenes (NHCs) and carbon disulfide. The monometallic Re(i) compounds were further coupled with Na[Re(CO)5] to afford bimetallic Re(0) species. Depending on the experimental conditions, either octacarbonyl dimers [Re2(CO)8(μ2-κ(1)-S,κ(1)-S'-S2C·NHC)] or hexacarbonyl clusters [Re2(CO)6(κ(2)-S,S'-κ(3)-S,C,S'-S2C·NHC)] were isolated. All the products were fully characterized using various analytical techniques. Single crystal XRD analysis helped establish with certainty the various binding modes exhibited by the NHC·CS2 ligands. With bite angles ranging from ca. 104 to 130°, these zwitterions displayed a remarkable flexibility, which also permitted significant twists of the thiometallated rings to preserve a staggered arrangement of the carbonyl groups in the bimetallic systems. Monitoring the chemical shift of the CS2(-) moiety by (13)C NMR spectroscopy was most useful to detect its change of hapticity upon decarbonylation of the octacarbonyl compounds into hexacarbonyl derivatives. IR spectroscopy was another very convenient tool to identify the type of complex formed in a reaction, based on the pattern of its carbonyl vibration bands. Advanced mass spectrometry techniques showed that all the compounds underwent partial or total decarbonylation in the gas phase with no concomitant fragmentation of the bimetallic assemblies into monometallic ions.

  3. Mono- and bimetallic manganese-carbonyl complexes and clusters bearing imidazol(in)ium-2-dithiocarboxylate ligands.

    PubMed

    Beltrán, Tomás F; Zaragoza, Guillermo; Delaude, Lionel

    2017-02-14

    Five complexes with the generic formula fac-[MnBr(CO)3(S2C·NHC)] were obtained by reacting [MnBr(CO)5] with a set of representative imidazol(in)ium-2-dithiocarboxylate zwitterions. These ligands are the adducts of N-heterocyclic carbenes (NHCs) and carbon disulfide. The mononuclear Mn(i) derivatives were coupled with Na[Mn(CO)5] to afford bimetallic [Mn2(CO)6(S2C·NHC)] clusters. Yet, the most convenient strategy to access these dinuclear Mn(0) products implied a direct carbonyl substitution from the [Mn2(CO)10] dimer. The molecular structures of three monometallic and four bimetallic compounds were elucidated by single crystal X-ray diffraction analysis. In the monometallic complexes, the NHC·CS2 ligands exhibited a bidentate κ(2)-S,S' coordination mode with an S-C-S bite angle of about 116°. In the dinuclear clusters, the CS2(-) unit acted as a chelate toward one manganese center and as a pseudoallylic ligand toward the other one. The S-C-S bite angle was reduced to ca. 104°. Thus, the zwitterions displayed a remarkable flexibility, which also permitted a staggered arrangement of the carbonyl groups in the bimetallic systems. Examination of the [small nu, Greek, macron]CO absorption bands on IR spectroscopy helped identify the presence of fac-Mn(CO)3 or Mn2(CO)6 motifs, while the (13)C NMR chemical shift of the CS2(-) moiety was a reliable indicator for monitoring its hapticity. Whereas the dinuclear clusters were air- and moisture-stable crystalline solids, mononuclear halido derivatives displayed only a limited stability under aerobic conditions. Both types of compounds underwent rather unselective, extensive fragmentations in the gas phase, in sharp contrast with the analogous rhenium derivatives that led to clean sequential decarbonylation processes upon collision-induced dissociation.

  4. Luminescent Re(I) Carbonyl Complexes as Trackable PhotoCORMs for CO delivery to Cellular Targets.

    PubMed

    Chakraborty, Indranil; Jimenez, Jorge; Sameera, W M C; Kato, Masako; Mascharak, Pradip K

    2017-03-06

    A family of Re(I) carbonyl complexes of general formula [ReX(CO)3(phen)](0/1+) (where X = Cl(-), CF3SO3(-), MeCN, PPh3, and methylimidazole) derived from 1,10-phenanthroline (phen) exhibits variable emission characteristics depending on the presence of the sixth ancillary ligand/group (X). All complexes but with X = MeCN exhibit moderate CO release upon irradiation with low-power UV light and are indefinitely stable in anaerobic/aerobic environment in solution as well as in solid state when kept under dark condition. These CO donors liberate three, one, or no CO depending on the nature of sixth ligand upon illumination as studied with the aid of time-dependent IR spectroscopy. Results of excited-state density functional theory (DFT) and time-dependent DFT calculations provided insight into the origin of the emission characteristics of these complexes. The luminescent rheinum(I) photoCORMs uniformly displayed efficient cellular internalization by the human breast adenocarcinoma cells, MDA-MB-231, while the complex with PPh3 as ancillary ligand showed moderate nuclear localization in addition to the cytosolic distribution. These species hold significant promise as theranostic photoCORMs (photoinduced CO releasing molecules), where the entry of the pro-drug can be tracked within the cellular matrices.

  5. The Chemistry of Mesitylgallium(3) Derivatives as Arene Ligands in Metal Carbonyl Complexes. Crystal and Molecular Structures of ((CO)3Mo(Eta 6- C6Me3H2))Ga(C6Me3H2)2 and ((CO)3Mo(Eta 6-C6Me3H2))2GA(C6Me3H2)

    DTIC Science & Technology

    1988-12-16

    useful neutral 6 6 6amphoteric ligands include PhB (NMe2 )2 , PhB (OMe)2 , PhB (C 5Ho10 ) and PhB (CH2CH(Me)C2H4 ) 6 . An anionic arene-transition metal...recrystallized from an appropriate solvent system. Synthesis of [(CO)3MoNes]2Ga~es. The complex [(CO) 3MoMes]2GaMes was prepared by refluxing a...2.22 (s, p-Me, 3 H); IR (DME, v(CO), cm- I) 1960 (sh, s), 1951 (vs), 1879 (vs). Anal. Caled: C, 50.35; H, 4.22. Found: C, 50.56; H, 4.24. Synthesis

  6. Apple phenolics as inhibitors of the carbonylation pathway during in vitro metal-catalyzed oxidation of myofibrillar proteins.

    PubMed

    Rysman, Tine; Utrera, Mariana; Morcuende, David; Van Royen, Geert; Van Weyenberg, Stephanie; De Smet, Stefaan; Estévez, Mario

    2016-11-15

    The effect of apple phenolics on the oxidative damage caused to myofibrillar proteins by an in vitro metal-catalyzed oxidation system was investigated. Three pure phenolic compounds (chlorogenic acid, (-)-epicatechin and phloridzin) and an apple peel extract were added to myofibrillar proteins in three concentrations (50, 100 and 200μM), and a blank treatment was included as a control. All suspensions were subjected to Fe(3+)/H2O2 oxidation at 37°C during 10days, and protein oxidation was evaluated as carbonylation (α-amino adipic and γ-glutamic semialdehydes) and Schiff base cross-links. Significant inhibition by apple phenolics was found as compared to the control treatment, with (-)-epicatechin being the most efficient antioxidant and phloridzin showing the weakest antioxidant effect. The higher concentrations of apple extract showed effective antioxidant activity against protein oxidation in myofibrillar proteins, emphasizing the potential of apple by-products as natural inhibitors of protein oxidation in meat products. Copyright © 2016 Elsevier Ltd. All rights reserved.

  7. Single-Site Zeolite-Anchored Organoiridium Carbonyl Complexes: Characterization of Structure and Reactivity by Spectroscopy and Computational Chemistry

    DOE PAGES

    Martinez-Macias, Claudia; Chen, Mingyang; Dixon, David A.; ...

    2015-07-03

    We formed a family of HY zeolite-supported cationic organoiridium carbonyl complexes by reaction of Ir(CO)2(acac) (acac=acetylacetonate) to form supported Ir(CO)2 complexes, which were treated at 298K and 1atm with flowing gas-phase reactants, including C2H4, H2, (CO)-C-12, (CO)-C-13, and D2O. Mass spectrometry was used to identify effluent gases, and infrared and X-ray absorption spectroscopies were used to characterize the supported species, with the results bolstered by DFT calculations. The support is crystalline and presents a nearly uniform array of bonding sites for the iridium species, so these were characterized by a high degree of uniformity, which allowed a precise determination ofmore » the species involved in the replacement, for example, of one CO ligand of each Ir(CO)2 complex with ethylene. The supported species include the following: Ir(CO)2, Ir(CO)(C2H4)2, Ir(CO)(C2H4), Ir(CO)(C2H5), and (tentatively) Ir(CO)(H). The data determine a reaction network involving all of these species.« less

  8. Single-Site Zeolite-Anchored Organoiridium Carbonyl Complexes: Characterization of Structure and Reactivity by Spectroscopy and Computational Chemistry.

    PubMed

    Martinez-Macias, Claudia; Chen, Mingyang; Dixon, David A; Gates, Bruce C

    2015-08-10

    A family of HY zeolite-supported cationic organoiridium carbonyl complexes was formed by reaction of Ir(CO)2 (acac) (acac=acetylacetonate) to form supported Ir(CO)2 complexes, which were treated at 298 K and 1 atm with flowing gas-phase reactants, including C2 H4 , H2 , (12) CO, (13) CO, and D2 O. Mass spectrometry was used to identify effluent gases, and infrared and X-ray absorption spectroscopies were used to characterize the supported species, with the results bolstered by DFT calculations. Because the support is crystalline and presents a nearly uniform array of bonding sites for the iridium species, these were characterized by a high degree of uniformity, which allowed a precise determination of the species involved in the replacement, for example, of one CO ligand of each Ir(CO)2 complex with ethylene. The supported species include the following: Ir(CO)2 , Ir(CO)(C2 H4)2 , Ir(CO)(C2 H4), Ir(CO)(C2 H5), and (tentatively) Ir(CO)(H). The data determine a reaction network involving all of these species.

  9. Single-Site Zeolite-Anchored Organoiridium Carbonyl Complexes: Characterization of Structure and Reactivity by Spectroscopy and Computational Chemistry

    SciTech Connect

    Martinez-Macias, Claudia; Chen, Mingyang; Dixon, David A.; Gates, Bruce C.

    2015-07-03

    We formed a family of HY zeolite-supported cationic organoiridium carbonyl complexes by reaction of Ir(CO)2(acac) (acac=acetylacetonate) to form supported Ir(CO)2 complexes, which were treated at 298K and 1atm with flowing gas-phase reactants, including C2H4, H2, (CO)-C-12, (CO)-C-13, and D2O. Mass spectrometry was used to identify effluent gases, and infrared and X-ray absorption spectroscopies were used to characterize the supported species, with the results bolstered by DFT calculations. The support is crystalline and presents a nearly uniform array of bonding sites for the iridium species, so these were characterized by a high degree of uniformity, which allowed a precise determination of the species involved in the replacement, for example, of one CO ligand of each Ir(CO)2 complex with ethylene. The supported species include the following: Ir(CO)2, Ir(CO)(C2H4)2, Ir(CO)(C2H4), Ir(CO)(C2H5), and (tentatively) Ir(CO)(H). The data determine a reaction network involving all of these species.

  10. Photochemistry of Metal-Metal Bonded Transition Element Complexes

    DTIC Science & Technology

    1980-12-12

    CONTRACT NO0014-75-C-0880 Task No. NR 051-579 TECHNICAL REPORT NO. 25 PHOTOCHEMISTRY OF METAL-METAL BONDED TRANSITION ELEMENT COMPLEXES by Mark S . Wrighton...unlimited. 17, Di:- t. Ii t I / Avolil:J, ; Codc’s ! Photochemistry of Metal-Metal Bonded Transition Element Complexes Mark S . Wrighton, James L. Graff...publication in the ACS Symposium Series, "Reactivity of MetalrMetal Bonds", M. H. Chisholm, ed.) IA c*Addre~ s orrespondence to this author, ; r[ I . - - 1

  11. High-nuclearity ruthenium carbonyl cluster complexes derived from 2-amino-6-methylpyridine: synthesis of nonanuclear derivatives containing mu4- and mu5-oxo ligands.

    PubMed

    Cabeza, Javier A; del Río, Ignacio; García-Alvarez, Pablo; Miguel, Daniel

    2006-07-24

    Nonanuclear cluster complexes [Ru9(mu3-H)2(mu-H)(mu5-O)(mu4-ampy)(mu3-Hampy)(CO)21] (4) (H2ampy = 2-amino-6-methylpyridine), [Ru9(mu5-O)2(mu4-ampy)(mu3-Hampy)2(mu-CO)(CO)20] (5), [Ru9(mu5-O)2(mu4-ampy)(mu3-Hampy)2(mu-CO)2(CO)19] (6), and [Ru9(mu4-O)(mu5-O)(mu4-ampy)(mu3-Hampy)(mu-Hampy)(mu-CO)(CO)19] (7), together with the known hexanuclear [Ru6(mu3-H)2(mu5-ampy)(mu-CO)2(CO)14] (2) and the novel pentanuclear [Ru5(mu4-ampy)(2)(mu-CO)(CO)12] (3) complexes, are products of the thermolysis of [Ru3(mu-H)(mu3-Hampy)(CO)9] (1) in decane at 150 degrees C. Two different and very unusual quadruply bridging coordination modes have been observed for the ampy ligand. Compounds 4-7 also feature one (4) or two (5-7) bridging oxo ligands. With the exception of one of the oxo ligands of 7, which is in a distorted tetrahedral environment, the remaining oxo ligands of 4-7 are surrounded by five metal atoms. In carbonyl metal clusters, quadruply bridging oxo ligands are very unusual, whereas quintuply bridging oxo ligands are unprecedented. By using 18O-labeled water, we have unambiguously established that these oxo ligands arise from water.

  12. Prebiotic coordination chemistry: The potential role of transition-metal complexes in the chemical evolution

    NASA Technical Reports Server (NTRS)

    Beck, M.

    1979-01-01

    In approaching the extremely involved and complex problem of the origin of life, consideration of the coordination chemistry appeared not only as a possibility but as a necessity. The first model experiments appear to be promising because of prebiotic-type synthesis by means of transition-metal complexes. It is especially significant that in some instances various types of vitally important substances (nucleic bases, amino acids) are formed simultaneously. There is ground to hope that systematic studies in this field will clarify the role of transition-metal complexes in the organizatorial phase of chemical evolution. It is obvious that researchers working in the fields of the chemistry of cyano and carbonyl complexes, and of the catalytic effect of transition-metal complexes are best suited to study these aspects of the attractive and interesting problem of the origin of life.

  13. Chemical bonding of hydrogen molecules to transition metal complexes

    SciTech Connect

    Kubas, G.J.

    1990-01-01

    The complex W(CO){sub 3}(PR{sub 3}){sub 2}(H{sub 2}) (CO = carbonyl; PR{sub 3} = organophosphine) was prepared and was found to be a stable crystalline solid under ambient conditions from which the hydrogen can be reversibly removed in vacuum or under an inert atmosphere. The weakly bonded H{sub 2} exchanges easily with D{sub 2}. This complex represents the first stable compound containing intermolecular interaction of a sigma-bond (H-H) with a metal. The primary interaction is reported to be donation of electron density from the H{sub 2} bonding electron pair to a vacant metal d-orbital. A series of complexes of molybdenum of the type Mo(CO)(H{sub 2})(R{sub 2}PCH{sub 2}CH{sub 2}PR{sub 2}){sub 2} were prepared by varying the organophosphine substitutent to demonstrate that it is possible to bond either dihydrogen or dihydride by adjusting the electron-donating properties of the co-ligands. Results of infrared and NMR spectroscopic studies are reported. 20 refs., 5 fig.

  14. Carbonyl sulfide

    Integrated Risk Information System (IRIS)

    Carbonyl sulfide ; CASRN 463 - 58 - 1 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncarcinogenic

  15. Nickel carbonyl

    Integrated Risk Information System (IRIS)

    Nickel carbonyl ; CASRN 13463 - 39 - 3 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncarcinogenic

  16. Asymmetric 1,3-Dipolar Cycloaddition Reactions Catalyzed by Heterocycle-Based Metal Complexes

    NASA Astrophysics Data System (ADS)

    Suga, Hiroyuki

    Highly enantioselective 1,3-dipolar cycloaddition reactions of several 1,3-dipoles, such as nitrones, nitrile oxides, nitrile imines, diazoalkanes, azomethine imines and carbonyl ylides, catalyzed by heterocyclic supramolecular type of metal complexes consisting of chiral heterocyclic compounds and metal salts were described in terms of their ability of asymmetric induction and enantioface differentiation. The scope and limitations of each cycloaddition reactions were also briefly described. Of the chiral hererocycle-based ligands, chiral bisoxazoline, 2,6-bis(oxazolinyl)pyridine, and related oxazoline ligands are shown to be quite effective in obtaining high levels of asymmtric induction. The combination of the bisoxazoline ligand derived from (1S,2R)-cis-1-amino-2-indanol and metal salts was especially efficient for asymmetric cycloaddition reactions of a number of 1,3-dipoles, such as nitrones, nitrile oxide, nitrile imines, diazoacetates and azomethine imines. The metals utilized for the heterocycle-based complexes show a crucial role for degree of asymmetric induction depending upon the 1,3-dipole used. High levels of enantioselectivity were achieved in 1,3-dipolar cycloaddition reactions of unstable carbonyl ylides with benzyloxyacetaldehyde derivatives, α-keto esters, 3-(2-alkenoyl)-2-oxazolidinones, and even vinyl ethers, which were catalyzed by Pybox-lanthanoid metal complexes.

  17. Halide, amide, cationic, manganese carbonylate, and oxide derivatives of triamidosilylamine uranium complexes.

    PubMed

    Gardner, Benedict M; Lewis, William; Blake, Alexander J; Liddle, Stephen T

    2011-10-03

    Treatment of the complex [U(Tren(TMS))(Cl)(THF)] [1, Tren(TMS) = N(CH(2)CH(2)NSiMe(3))(3)] with Me(3)SiI at room temperature afforded known crystalline [U(Tren(TMS))(I)(THF)] (2), which is reported as a new polymorph. Sublimation of 2 at 160 °C and 10(-6) mmHg afforded the solvent-free dimer complex [{U(Tren(TMS))(μ-I)}(2)] (3), which crystallizes in two polymorphic forms. During routine preparations of 1, an additional complex identified as [U(Cl)(5)(THF)][Li(THF)(4)] (4) was isolated in very low yield due to the presence of a slight excess of [U(Cl)(4)(THF)(3)] in one batch. Reaction of 1 with one equivalent of lithium dicyclohexylamide or bis(trimethylsilyl)amide gave the corresponding amide complexes [U(Tren(TMS))(NR(2))] (5, R = cyclohexyl; 6, R = trimethylsilyl), which both afforded the cationic, separated ion pair complex [U(Tren(TMS))(THF)(2)][BPh(4)] (7) following treatment of the respective amides with Et(3)NH·BPh(4). The analogous reaction of 5 with Et(3)NH·BAr(f)(4) [Ar(f) = C(6)H(3)-3,5-(CF(3))(2)] afforded, following addition of 1 to give a crystallizable compound, the cationic, separated ion pair complex [{U(Tren(TMS))(THF)}(2)(μ-Cl)][BAr(f)(4)] (8). Reaction of 7 with K[Mn(CO)(5)] or 5 or 6 with [HMn(CO)(5)] in THF afforded [U(Tren(TMS))(THF)(μ-OC)Mn(CO)(4)] (9); when these reactions were repeated in the presence of 1,2-dimethoxyethane (DME), the separated ion pair [U(Tren(TMS))(DME)][Mn(CO)(5)] (10) was isolated instead. Reaction of 5 with [HMn(CO)(5)] in toluene afforded [{U(Tren(TMS))(μ-OC)(2)Mn(CO)(3)}(2)] (11). Similarly, reaction of the cyclometalated complex [U{N(CH(2)CH(2)NSiMe(2)Bu(t))(2)(CH(2)CH(2)NSiMeBu(t)CH(2))}] with [HMn(CO)(5)] gave [{U(Tren(DMSB))(μ-OC)(2)Mn(CO)(3)}(2)] [12, Tren(DMSB) = N(CH(2)CH(2)NSiMe(2)Bu(t))(3)]. Attempts to prepare the manganocene derivative [U(Tren(TMS))MnCp(2)] from 7 and K[MnCp(2)] were unsuccessful and resulted in formation of [{U(Tren(TMS))}(2)(μ-O)] (13) and [MnCp(2)]. Complexes 3-13 have been

  18. Cobalt carbonyl complexes as probes for alkyne-tagged lipids[S

    PubMed Central

    Tallman, Keri A.; Armstrong, Michelle D.; Milne, Stephen B.; Marnett, Lawrence J.; Brown, H. Alex; Porter, Ned A.

    2013-01-01

    Monitoring lipid distribution and metabolism in cells and biological fluids poses many challenges because of the many molecular species and metabolic pathways that exist. This study describes the synthesis and study of molecules that contain an alkyne functional group as surrogates for natural lipids in cultured cells. Thus, hexadec-15-ynoic and hexadec-7-ynoic acids were readily incorporated into RAW 264.7 cells, principally as phosphocholine esters; the alkyne was used as a “tag” that could be transformed to a stable dicobalt-hexacarbonyl complex; and the complex could then be detected by HPLC/MS or HPLC/UV349nm. The 349 nm absorbance of the cobalt complexes was used to provide qualitative and quantitative information about the distribution and cellular concentrations of the alkyne lipids. The alkyne group could also be used as an affinity tag for the lipids by a catch-and-release strategy on phosphine-coated silica beads. Lipid extracts were enriched in the tagged lipids in this way, making the approach of potential utility to study lipid transformations in cell culture. Both terminal alkynes and internal alkynes were used in this affinity “pull-down” strategy. This method facilitates measuring lipid species that might otherwise fall below limits of detection. PMID:23307946

  19. Protein tyrosine phosphatase inhibition by metals and metal complexes.

    PubMed

    Lu, Liping; Zhu, Miaoli

    2014-05-10

    Protein tyrosine phosphatases (PTPs) play essential roles in controlling cell proliferation, differentiation, communication, and adhesion. The dysregulated activities of PTPs are involved in the pathogenesis of a number of human diseases such as cancer, diabetes, and autoimmune diseases. Many PTPs have emerged as potential new targets for novel drug discovery. PTP inhibitors have attracted much attention. Many PTP inhibitors have been developed. Some of them have been proven to be efficient in lowering blood glucose levels in vivo or inhibiting tumor xenograft growth. Some metal ions and metal complexes potently inhibit PTPs. The metal atoms within metal complexes play an important role in PTP binding, while ligand structures influence the inhibitory potency and selectivity. Some metal complexes can penetrate the cell membrane and selectively bind to their targeting PTPs, enhancing the phosphorylation of the related substrates and influencing cellular metabolism. PTP inhibition is potentially involved in the pathophysiological and toxicological processes of metals and some PTPs may be cellular targets of certain metal-based therapeutic agents. Investigating the structural basis of the interactions between metal complexes and PTPs would facilitate a comprehensive understanding of the structure-activity relationship and accelerate the development of promising metal-based drugs targeting specific PTPs.

  20. Efficient light-harvesting using non-carbonyl carotenoids: Energy transfer dynamics in the VCP complex from Nannochloropsis oceanica.

    PubMed

    Keşan, Gürkan; Litvín, Radek; Bína, David; Durchan, Milan; Šlouf, Václav; Polívka, Tomáš

    2016-04-01

    Violaxanthin-chlorophyll a protein (VCP) from Nannochloropsis oceanica is a Chl a-only member of the LHC family of light-harvesting proteins. VCP binds carotenoids violaxanthin (Vio), vaucheriaxanthin (Vau), and vaucheriaxanthin-ester (Vau-ester). Here we report on energy transfer pathways in the VCP complex. The overall carotenoid-to-Chla energy transfer has efficiency over 90%. Based on their energy transfer properties, the carotenoids in VCP can be divided into two groups; blue carotenoids with the lowest energy absorption band around 480nm and red carotenoids with absorption extended up to 530nm. Both carotenoid groups transfer energy efficiently from their S2 states, reaching efficiencies of ~70% (blue) and ~60% (red). The S1 pathway, however, is efficient only for the red carotenoid pool for which two S1 routes characterized by 0.33 and 2.4ps time constants were identified. For the blue carotenoids the S1-mediated pathway is represented only by a minor route likely involving a hot S1 state. The relaxed S1 state of blue carotenoids decays to the ground state within 21ps. Presence of a fraction of non-transferring red carotenoids with the S1 lifetime of 13ps indicates some specific carotenoid-protein interaction that must shorten the intrinsic S1 lifetime of Vio and/or Vau whose S1 lifetimes in methanol are 26 and 29ps, respectively. The VCP complex from N. oceanica is the first example of a light-harvesting complex binding only non-carbonyl carotenoids with carotenoid-to-chlorophyll energy transfer efficiency over 90%. Copyright © 2015 Elsevier B.V. All rights reserved.

  1. Unusual structures and reactivity of mixed metal cluster complexes containing the palladium/platinum tri-t-butylphosphine grouping.

    PubMed

    Adams, Richard D; Captain, Burjor

    2009-03-17

    Polynuclear metal carbonyl complexes have a range of applications in chemical research: for example, they can serve as surface models to probe features of heterogeneous catalysis and can perform novel transformations of organic molecules in solutions. Mixed metal complexes can demonstrate bimetallic cooperativity and synergism and can also serve as precursors to multimetallic heterogeneous catalysts that have superior activities and selectivities. This Account describes the results of our recent comprehensive study of the chemistry of mixed metal cluster complexes containing the sterically encumbered M(PBu(t)(3)), M = Pd or Pt, group. This grouping readily adds to the metal-metal bonds of metal carbonyl cluster complexes and modifies their reactivity. We have prepared new, highly electronically unsaturated mixed metal complexes that exhibit unusually high reactivity toward hydrogen. The platinum atom of the Pt(PBu(t)(3)) grouping can bond to as many as five metal atoms, and it can interconvert, sometimes rapidly, between the different bonding modes. The large steric effects of the PBu(t)(3) ligand allowed us to prepare highly unsaturated, stable, mixed-metal complexes, and these complexes react with hydrogen, sometimes reversibly, under very mild conditions to yield polyhydride complexes. Strong evidence suggests that the Pt(PBu(t)(3)) group can also activate metal-hydrogen bonds in other complexes. In the future, we expect that researchers will prepare a greater variety of mixed metal complexes containing the Pd/Pt(PBu(t)(3)) group or other similar bulky groups, and that some of these complexes will exhibit even more unusual chemistry than what we have observed so far.

  2. Recent developments in complex metal oxide photoelectrodes

    NASA Astrophysics Data System (ADS)

    Abdi, Fatwa F.; Berglund, Sean P.

    2017-05-01

    Photoelectrochemical (PEC) water splitting, a process that directly produces hydrogen from water and sunlight using semiconductor materials, is an attractive form of renewable energy production. The hydrogen that is produced can be easily transported, stored, and utilized as a fuel without the emission of greenhouse gasses. However, many scientific and engineering challenges need to be overcome before PEC water splitting can be implemented on a large scale. One of the biggest challenges is the identification of suitable semiconductor materials to use in the construction of photoelectrodes. This topical review highlights a promising class of materials, complex metal oxides, which can be used as photoelectrodes for PEC water splitting. The advantages and limitations of complex metal oxides are first discussed, and strategies to overcome the limitations are outlined using the model case of bismuth vanadate (BiVO4), one of the highest performing complex metal oxide photoanodes reported to date. Building on the success story of BiVO4, we discuss pathways towards achieving even higher water splitting performance, including bandgap engineering as well as the development of alternative complex metal oxides with more appropriate bandgaps for obtaining high solar-to-hydrogen efficiency. Several classes of complex metal oxides (e.g. delafossites, tungstates, vanadates, spinels) are presented as promising candidates for photoelectrode materials. Finally, we conclude by summarizing the key properties of these complex metal oxides and providing an outlook towards expedited discovery of new and novel complex metal oxides for use as photoelectrodes.

  3. Nucleophilic ring opening of bridging thietane ligands in trirhenium carbonyl cluster complexes

    SciTech Connect

    Adams, R.D.; Cortopassi, J.E.; Falloon, S.B.

    1992-11-01

    The reactions of 3,3-dimethylthietane, SCH{sub 2}CMe{sub 2}CH{sub 2} (3,3-DMT), and thietane, SCH{sub 2}CH{sub 2}CH{sub 2}, with Re{sub 3}(CO){sub 10}[{mu}-SCH{sub 2}CH{sub 2}CH{sub 2}]({mu}-H){sub 3}, 2b. Compound 2a was characterized crystallographically and was found to consist of a trirhenium cluster with three bridging hydride ligands and a bridging thietane ligand coordinated through its sulfur atom. 2a and 2b react with halide ions by ring-opening additions to the 3,3-DMT ligand to yield the complex anions [Re{sub 3}(CO){sub 10}({mu}-SCH{sub 2}CMe{sub 2}CH{sub 2}x)({mu}-h){sub 3}]{sup -} 3A-6A, X = F (71%), Cl(71%), Br(84%), I(87%) and [Re{sub 3}(CO){sub 10}({mu}-SCH{sub 2}CH{sub 2}CH{sub 2}Cl)({mu}-H){sub 3}]{sup -}, 4b (67%). Similarly, addition of NMe{sub 3} to 2a and 2b yielded the ring-opened zwitterions Re{sub 3}(CO){sub 10}({mu}-SCH{sub 2}CMe{sub 2}CH{sub 2}NMe{sub 3})({mu}-H){sub 3}, 7 a crystographically. They are zwitterions positively charged at the nitrogen atoms and negatively charged on the trirhenium clusters. Complex 7b was also obtained in a 48% yield from the reaction of Re{sub 3}(C){sub 12}({mu}-H){sub 3} with Me{sub 3}NO in the presence of thietane, but the corresponding reaction using 3,3-DMT yielded only 2a and Re{sub 3}(CO){sub 11}(SCH{sub 2}CMe{sub 2}CH{sub 2})({mu}-H){sub 3}, 8. Attempts to obtain a ring-opening addition to 2a by reaction with PMe{sub 2}Ph yielded only Re{sub 3}(CO){sub 10}(PMe{sub 2}PH){sub 2}({mu}-H){sub 3} by ligand substitution. Attempts to obtain ring opening addition to 8 by reaction with I{sup -} yielded only [Re{sub 3}(CO){sub 11}I({mu}-H){sub 3}]{sup -} by ligand substitution. 20 refs., 3 figs., 10 tabs.

  4. An insight into fluorescent transition metal complexes.

    PubMed

    Chia, Y Y; Tay, M G

    2014-09-21

    The emission from transition metal complexes is usually produced from triplet excited states. Owing to strong spin-orbit coupling (SOC), the fast conversion of singlet to triplet excited states via intersystem crossing (ISC) is facilitated. Hence, in transition metal complexes, emission from singlet excited states is not favoured. Nevertheless, a number of examples of transition metal complexes that fluoresce with high intensity have been found and some of them were even comprehensively studied. In general, three common photophysical characteristics are used for the identification of fluorescent emission from a transition metal complex: emission lifetimes on the nanosecond scale; a small Stokes shift; and intense emission under aerated conditions. For most of the complexes reviewed here, singlet emission is the result of ligand-based fluorescence, which is the dominant emission process due to poor metal-ligand interactions leading to a small metal contribution in the excited states, and a competitive fluorescence rate constant when compared to the ISC rate constant. In addition to the pure fluorescence from metal complexes, another two types of fluorescent emissions were also reviewed, namely, delayed fluorescence and fluorescence-phosphorescence dual emissions. Both emissions also have their respective unique characteristics, and thus they are discussed in this perspective.

  5. Reactivity of a rhenium hydroxo-carbonyl complex toward carbon disulfide: insights from theory.

    PubMed

    Yeguas, Violeta; Campomanes, Pablo; López, Ramón

    2010-01-21

    The reaction mechanism on the formation of the hydrosulfido complex [Re(SH)(CO)(3)(bipy)] via the reaction of [Re(OH)(CO)(3)(bipy)] with carbon disulfide was theoretically investigated at the B3LYP/6-31+G(d,p) (LANL2DZ+f for Re) level of theory taking into account bulk solvent effects by using the PCM-UAHF continuum model. The energetics of the process was also analyzed by means of single-point energy calculations by replacing the B3LYP functional by the B3PW91, M05, TPSS and TPSSh ones. The most favored mechanistic routes obtained by us uncover all the molecular rearrangements involved in the reactive process, thus allowing the enriching of the experimental mechanistic proposal. Besides, our findings permit to explain the assignment of the solution color change to the formation of [Re(SH)(CO)(3)(bipy)] when mixed CS(2) with [Re(OH)(CO)(3)(bipy)]. Finally, based on our mechanistic study is also possible to rationalize the formation of [Re(SC(S)OCH(3))(CO)(3)(bipy)] when [Re(OCH(3))(CO)(3)(bipy)] reacts with CS(2) and of TpZn-OCH(3) when methanol is present in the reaction of TpZn-OH with CS(2).

  6. Group 4 Metalloporphyrin diolato Complexes and Catalytic Application of Metalloporphyrins and Related Transition Metal Complexes

    SciTech Connect

    Du, Guodong

    2003-01-01

    In this work, the first examples of group 4 metalloporphyrin 1,2-diolato complexes were synthesized through a number of strategies. In general, treatment of imido metalloporphyrin complexes, (TTP)M=NR, (M = Ti, Zr, Hf), with vicinal diols led to the formation of a series of diolato complexes. Alternatively, the chelating pinacolate complexes could be prepared by metathesis of (TTP)MCl2 (M = Ti, Hf) with disodium pinacolate. These complexes were found to undergo C-C cleavage reactions to produce organic carbonyl compounds. For titanium porphyrins, treatment of a titanium(II) alkyne adduct, (TTP)Ti(η2-PhC≡CPh), with aromatic aldehydes or aryl ketones resulted in reductive coupling of the carbonyl groups to produce the corresponding diolato complexes. Aliphatic aldehydes or ketones were not reactive towards (TTP)Ti(η2-PhC≡CPh). However, these carbonyl compounds could be incorporated into a diolato complex on reaction with a reactive precursor, (TTP)Ti[O(Ph)2C(Ph)2O] to provide unsymmetrical diolato complexes via cross coupling reactions. In addition, an enediolato complex (TTP)Ti(OCPhCPhO) was obtained from the reaction of (TTP)Ti(η2-PhC≡CPh) with benzoin. Titanium porphyrin diolato complexes were found to be intermediates in the (TTP)Ti=O-catalyzed cleavage reactions of vicinal diols, in which atmospheric oxygen was the oxidant. Furthermore, (TTP)Ti=O was capable of catalyzing the oxidation of benzyl alcohol and α-hydroxy ketones to benzaldehyde and α-diketones, respectively. Other high valent metalloporphyrin complexes also can catalyze the oxidative diol cleavage and the benzyl alcohol oxidation reactions with dioxygen. A comparison of Ti(IV) and Sn(IV) porphyrin chemistry was undertaken. While chelated diolato complexes were invariably obtained for titanium porphyrins on treatment with 1,2-diols, the reaction of vicinal diols with tin porphyrins gave a number of products, including mono

  7. Regiospecific carbonylative annulation of iodophenol acetates and acetylenes to construct the flavones by a new catalyst of palladium-thiourea-dppp complex.

    PubMed

    Miao, H; Yang, Z

    2000-06-15

    [reaction: see text] Regiospecific carbonylative annulation of o-iodophenol acetates and acetylenes mediated by palladium-thiourea-dppp complex in the presence of base at 40 degrees C under a balloon pressure of CO generates diversified flavones in high yields. This newly developed synthetic technology provides a highly efficient method for potential application to the combinatorial synthesis of those heterocycles on the solid support.

  8. Lack of FTSH4 Protease Affects Protein Carbonylation, Mitochondrial Morphology, and Phospholipid Content in Mitochondria of Arabidopsis: New Insights into a Complex Interplay.

    PubMed

    Smakowska, Elwira; Skibior-Blaszczyk, Renata; Czarna, Malgorzata; Kolodziejczak, Marta; Kwasniak-Owczarek, Malgorzata; Parys, Katarzyna; Funk, Christiane; Janska, Hanna

    2016-08-01

    FTSH4 is one of the inner membrane-embedded ATP-dependent metalloproteases in mitochondria of Arabidopsis (Arabidopsis thaliana). In mutants impaired to express FTSH4, carbonylated proteins accumulated and leaf morphology was altered when grown under a short-day photoperiod, at 22°C, and a long-day photoperiod, at 30°C. To provide better insight into the function of FTSH4, we compared the mitochondrial proteomes and oxyproteomes of two ftsh4 mutants and wild-type plants grown under conditions inducing the phenotypic alterations. Numerous proteins from various submitochondrial compartments were observed to be carbonylated in the ftsh4 mutants, indicating a widespread oxidative stress. One of the reasons for the accumulation of carbonylated proteins in ftsh4 was the limited ATP-dependent proteolytic capacity of ftsh4 mitochondria, arising from insufficient ATP amount, probably as a result of an impaired oxidative phosphorylation (OXPHOS), especially complex V. In ftsh4, we further observed giant, spherical mitochondria coexisting among normal ones. Both effects, the increased number of abnormal mitochondria and the decreased stability/activity of the OXPHOS complexes, were probably caused by the lower amount of the mitochondrial membrane phospholipid cardiolipin. We postulate that the reduced cardiolipin content in ftsh4 mitochondria leads to perturbations within the OXPHOS complexes, generating more reactive oxygen species and less ATP, and to the deregulation of mitochondrial dynamics, causing in consequence the accumulation of oxidative damage.

  9. Lone pair⋯π interactions involving carbonyl π-systems: Experimental and theoretical study of the complexes of COF2 and COFCl with dimethyl ether

    NASA Astrophysics Data System (ADS)

    Geboes, Yannick; De Proft, Frank; Herrebout, Wouter A.

    2016-09-01

    In this theoretical and experimental study, the ability of carbonyl fluoride (COF2) and carbonyl chloride fluoride (COFCl) to form noncovalent interactions with the Lewis base dimethyl ether (DME) is assessed. From ab initio calculations, two stable complexes are found for COF2·DME, both formed through a lone pair⋯π interaction. FTIR measurements on liquefied noble gas solutions, supported by ab initio calculations, statistical thermodynamical calculations and Monte Carle Free Energy Perturbation calculations, show that a 1:1 lone pair⋯π bonded complex is found in solution, with an experimental complexation enthalpy of -14.5(3) kJ mol-1. For COFCl·DME three lone pair⋯π complexes, as well as a Cl⋯O halogen bonded complex, are found from ab initio calculations. Experimentally, clear complex bands for 1:1 lone pair⋯π complexes are observed, with an experimental complexation enthalpy of -11.4(2) kJ mol-1. Furthermore, indications of the presence of a small amount of the halogen bonded complex are also observed.

  10. Copper(II) complexes of N-(2-{[(2E)-2-(2-Hydroxy-(5-substituted)-benzylidene)-hydrazino]carbonyl}phenyl)benzamide ligands and heterocyclic coligands.

    PubMed

    Chavan, S S; Sawant, V A; Jadhav, A N

    2014-01-03

    Some copper(II) complexes of the type [Cu(L1-3)(phen]·CH2Cl2 (1a-3a) and [Cu(L1-3) (bipy)]·CH2Cl2 (1b-3b) (where L1=N-(2-{[(2E)-2-(2-Hydroxy-benzylidene)-hydrazino]carbonyl}phenyl)benzamide, L2=N-(2-{[(2E)-2-(2-Hydroxy-(5-bromo)-benzylidene)-hydrazino]carbonyl}phenyl)benzamide, L3=N-(2-{[(2E)-2-(2-Hydroxy-(5-methoxy)-benzylidene)-hydrazino]carbonyl}phenyl)benzamide; phen=1,10-phenanthroline, bipy=2,2'-bipyridine) have been prepared and characterized on the basis of elemental analyses, IR, UV-Vis and EPR spectral studies. IR spectra indicate that the ligand L1-3 exists in the keto form in the solid state, while at the time of complexation, it tautomerises into enol form. The single crystal X-ray diffraction study of the representative complex [Cu(L1) (phen)]·CH2Cl2 (1a) reveals the distorted square pyramidal geometry around copper(II). Crystal data of (1a): space group=P21/n, a=11.5691(16) Å, b=11.0885(15) Å, c=24.890(4) Å, V=3166.2(8) Å(3), Z=4. The electrochemical behavior of all the complexes indicate that the phen complexes appears at more positive potential as compared to those for bipy complexes, as a consequence of its stronger π acidic character. All the complexes exhibit blue-green emission as a result of the fluorescence from the intra-ligand (π→π(*)) emission excited state.

  11. STUDY OF METAL FLUORINE COMPLEXES.

    DTIC Science & Technology

    spectroscopy. These series consisted of fluorotitanate complexes of formula TiF4.2(donor) and TiF5.(donor)(-), where donor represents an organic molecule... fluorotitanate complexes. The temperature dependence of the TiF4.2D spectra was also studied. The low infrared spectra of some SnF4.2D and TiF4.2D were also obtained. (Author)

  12. Fabrication of complex metallic nanostructures by nanoskiving.

    PubMed

    Xu, Qiaobing; Rioux, Robert M; Whitesides, George M

    2007-10-01

    This paper describes the use of nanoskiving to fabricate complex metallic nanostructures by sectioning polymer slabs containing small, embedded metal structures. This method begins with the deposition of thin metallic films on an epoxy substrate by e-beam evaporation or sputtering. After embedding the thin metallic film in an epoxy matrix, sectioning (in a plane perpendicular or parallel to the metal film) with an ultramicrotome generates sections (which can be as thin as 50 nm) of epoxy containing metallic nanostructures. The cross-sectional dimensions of the metal wires embedded in the resulting thin epoxy sections are controlled by the thickness of the evaporated metal film (which can be as small as 20 nm) and the thickness of the sections cut by the ultramicrotome; this work uses a standard 45 degrees diamond knife and routinely generates slabs 50 nm thick. The embedded nanostructures can be transferred to, and positioned on, planar or curved substrates by manipulating the thin polymer film. Removal of the epoxy matrix by etching with an oxygen plasma generates free-standing metallic nanostructures. Nanoskiving can fabricate complex nanostructures that are difficult or impossible to achieve by other methods of nanofabrication. These include multilayer structures, structures on curved surfaces, structures that span gaps, structures in less familiar materials, structures with high aspect ratios, and large-area structures comprising two-dimensional periodic arrays. This paper illustrates one class of application of these nanostructures: frequency-selective surfaces at mid-IR wavelengths.

  13. Synthesis, physico-chemical characterization and antimicrobial activities of 3-methoxysalicylaldehyde-2-aminobenzoylhydrazone and its transition metal complexes

    NASA Astrophysics Data System (ADS)

    Badiger, Dayananda S.; Hunoor, Rekha S.; Patil, Basavaraj R.; Vadavi, Ramesh S.; Mangannavar, Chandrashekhar V.; Muchchandi, Iranna S.; Gudasi, Kalagouda B.

    2012-07-01

    The transition metal complexes of 3-methoxysalicylaldehyde-2-aminobenzhydrazone (H2L) were synthesized and characterized by various spectroscopic (IR, NMR, UV-Vis, mass), thermal and other physicochemical methods. The ligand acts both in monobasic as well as dibasic manner and coordinates in tridentate fashion with carbonyl oxygen, azomethine nitrogen and phenolic oxygen via deprotonation except in Cu(II) complex where the ligand coordinates via enolization and deprotonation of amide proton. An octahedral geometry was assigned for Mn(II), Co(II), Ni(II) and Zn(II) complexes and square planar for Cu(II) complex. The ligand and its metal complexes have been screened for their in vitro antimicrobial activities using serial dilution method. Metal complexes in general have exhibited better antibacterial and antifungal activity than the free ligand. The Cu(II) complex exhibited highest antimicrobial activity among the compounds tested.

  14. Alkane Soluble Transition Metal Complexes.

    DTIC Science & Technology

    1983-10-01

    Al I7 𔃼 AKANE SOLUBLE TRANSITION METAL COUP rA’(U ROYAL3 MIARY COL OF SCIENCE SHRIVENHAM (ENGLAND) DEP O CHEMISTRY AND METALLURGY F R HARTLEY OCT 83...Associate Investigator B.G. Murray Chemistry and Metallurgy Departmnt TeRylMilitary College of Science Shrlveahau ftindou1 Wiltshire, UK This work woo...Plenary lecture at the 17th International Conference on Coordination Chemistry , saw" 1376. 2. D.3. Webster, Ady. Oranometal Chbe., 1977, 15,147. 3

  15. Luminescent aryl-group eleven metal complexes.

    PubMed

    López-de-Luzuriaga, José M; Monge, Miguel; Olmos, M Elena

    2017-02-14

    Among the coinage metal complexes displaying luminescent properties, those bearing C-donor aryl ligands have an increasing part in the chemistry of these metals. These types of ligands confer a high kinetic and thermodynamic stability on the complexes, but they can also be involved in the photoluminescent behaviour of the complexes. The development of new aryl-containing complexes of group eleven metals, the study of their photoluminescent properties and their related properties and applications are discussed in this perspective. Among these, luminescent gold(i) and gold(iii) compounds are being intensively used for the development of new properties with potential applications such as, for instance, electroluminescence, triboluminescence, mechanochromism, aggregated induced emissions, quenching, luminescent liquid crystals, low molecular weight gelators and photocatalysts, among others.

  16. Characterization and activity of cephalosporin metal complexes.

    PubMed

    Auda, S H; Mrestani, Y; Fetouh, M I; Neubert, R H H

    2008-08-01

    Semi-synthetic cephalosporin antibiotics have structures similar to that of penicillins, and both groups of compounds are characterized by similar properties and determined by the same methods. Most antibiotics, including cephalosporins and their decomposition products, contain electron donor groups that can bind naturally occurring metal ions in vivo. Cephalosporin antibiotics exhibit a change in their toxicological properties and biological performance when they were tested as metal complexes. The proposed reason for such a behavior is the capability of chelate binding of the cephalosporins to the metals. In an attempt to understand the coordination mode of metals with cephalosporins, different spectroscopic techniques such as IR, UV-visible, NMR spectroscopy and voltammetric measurements were carried out to elucidate the structure of the metal-cephalosporin complexes. Synthesis, characterization and biological screening of the cephalosporins and of the cephalosporin-metal complexes are discussed in this review. However, little information is available on the influence of the metal ions on the pharmacokinetics of the cephalosporin derivatives.

  17. Novel Metals and Metal Complexes as Platforms for Cancer Therapy

    PubMed Central

    Frezza, Michael; Hindo, Sarmad; Chen, Di; Davenport, Andrew; Schmitt, Sara; Tomco, Dajena; Dou, Q. Ping

    2013-01-01

    Metals are essential cellular components selected by nature to function in several indispensable biochemical processes for living organisms. Metals are endowed with unique characteristics that include redox activity, variable coordination modes, and reactivity towards organic substrates. Due to their reactivity, metals are tightly regulated under normal conditions and aberrant metal ion concentrations are associated with various pathological disorders, including cancer. For these reasons, coordination complexes, either as drugs or prodrugs, become very attractive probes as potential anticancer agents. The use of metals and their salts for medicinal purposes, from iatrochemistry to modern day, has been present throughout human history. The discovery of cisplatin, cis-[PtII(NH3)2Cl2], was a defining moment which triggered the interest in platinum(II)- and other metal-containing complexes as potential novel anticancer drugs. Other interests in this field address concerns for uptake, toxicity, and resistance to metallodrugs. This review article highlights selected metals that have gained considerable interest in both the development and the treatment of cancer. For example, copper is enriched in various human cancer tissues and is a co-factor essential for tumor angiogenesis processes. However the use of copper-binding ligands to target tumor copper could provide a novel strategy for cancer selective treatment. The use of nonessential metals as probes to target molecular pathways as anticancer agents is also emphasized. Finally, based on the interface between molecular biology and bioinorganic chemistry the design of coordination complexes for cancer treatment is reviewed and design strategies and mechanisms of action are discussed. PMID:20337575

  18. Novel metals and metal complexes as platforms for cancer therapy.

    PubMed

    Frezza, Michael; Hindo, Sarmad; Chen, Di; Davenport, Andrew; Schmitt, Sara; Tomco, Dajena; Dou, Q Ping

    2010-06-01

    Metals are essential cellular components selected by nature to function in several indispensable biochemical processes for living organisms. Metals are endowed with unique characteristics that include redox activity, variable coordination modes, and reactivity towards organic substrates. Due to their reactivity, metals are tightly regulated under normal conditions and aberrant metal ion concentrations are associated with various pathological disorders, including cancer. For these reasons, coordination complexes, either as drugs or prodrugs, become very attractive probes as potential anticancer agents. The use of metals and their salts for medicinal purposes, from iatrochemistry to modern day, has been present throughout human history. The discovery of cisplatin, cis-[Pt(II) (NH(3))(2)Cl(2)], was a defining moment which triggered the interest in platinum(II)- and other metal-containing complexes as potential novel anticancer drugs. Other interests in this field address concerns for uptake, toxicity, and resistance to metallodrugs. This review article highlights selected metals that have gained considerable interest in both the development and the treatment of cancer. For example, copper is enriched in various human cancer tissues and is a co-factor essential for tumor angiogenesis processes. However the use of copper-binding ligands to target tumor copper could provide a novel strategy for cancer selective treatment. The use of nonessential metals as probes to target molecular pathways as anticancer agents is also emphasized. Finally, based on the interface between molecular biology and bioinorganic chemistry the design of coordination complexes for cancer treatment is reviewed and design strategies and mechanisms of action are discussed.

  19. Metal Complexes for Defense against Cyanide Intoxication

    DTIC Science & Technology

    1986-11-01

    cyanide toxicity might be compared with that of other asphyxiants, particularly carbon monoxide. Carbon monoxide forms a complex with hemoglobin... carbon monoxide is present to disrupt the oxygen transport to the tissue. However, cyanide is toxic at much lower concentrations. According to ligand... carbon to an empty d-orbital on the metal, plus a it-bond, which is formed by the back-donation of a filled metal d-orbital to the empty antibonding

  20. Special issue: practical applications of metal complexes.

    PubMed

    Turel, Iztok

    2015-04-30

    In 1913 Alfred Werner received the Nobel Prize in Chemistry for his work that was of great importance for the development of coordination chemistry. In the years that followed numerous complexes consisting of metal ions and organic ligands were isolated, thus building a strong connection between inorganic and organic chemistry. Coordination compounds have many interesting properties which find diverse applications in numerous aspects of human life. Fourteeen contributions were received for this Special Issue covering very different aspects of metal complexes and their practical applications. The highest number of manuscripts deals with the biological activity of complexes which might potentially be used in the clinical practice. Authors have tested their cytotoxicity, antibacterial activity and enzyme inhibition. Their optical properties were studied in view of their potential use in photodynamic therapy. Moreover, optical properties could also be used for bioanalysis. It is also known that metal complexes are useful catalysts and a few such examples are also described herein. Many other interesting properties and facts about the isolated and described complexes are also reported (radioactivity, design of metal-organic frameworks, etc.).

  1. Biomimetic cavity-based metal complexes.

    PubMed

    Rebilly, Jean-Noël; Colasson, Benoit; Bistri, Olivia; Over, Diana; Reinaud, Olivia

    2015-01-21

    The design of biomimetic complexes for the modeling of metallo-enzyme active sites is a fruitful strategy for obtaining fundamental information and a better understanding of the molecular mechanisms at work in Nature's chemistry. The classical strategy for modeling metallo-sites relies on the synthesis of metal complexes with polydentate ligands that mimic the coordination environment encountered in the natural systems. However, it is well recognized that metal ion embedment in the proteic cavity has key roles not only in the recognition events but also in generating transient species and directing their reactivity. Hence, this review focuses on an important aspect common to enzymes, which is the presence of a pocket surrounding the metal ion reactive sites. Through selected examples, the following points are stressed: (i) the design of biomimetic cavity-based complexes, (ii) their corresponding host-guest chemistry, with a special focus on problems related to orientation and exchange mechanisms of the ligand within the host, (iii) cavity effects on the metal ion binding properties, including 1st, 2nd, and 3rd coordination spheres and hydrophobic effects and finally (iv) the impact these factors have on the reactivity of embedded metal ions. Important perspectives lie in the use of this knowledge for the development of selective and sensitive probes, new reactions, and green and efficient catalysts with bio-inspired systems.

  2. First row transition metal complexes of (E)-2-(2-(2-hydroxybenzylidene) hydrazinyl)-2-oxo-N-phenylacetamide complexes

    NASA Astrophysics Data System (ADS)

    Yousef, T. A.; Abu El-Reash, G. M.; Rakha, T. H.; El-Ayaan, Usama

    2011-12-01

    Manganese(II), iron(II), cobalt(II), nickel(II), copper(II), and chromium(III) complexes of (E)-2-(2-(2-hydroxybenzylidene)hydrazinyl)-2-oxo-N-phenylacetamide were synthesized and characterized by elemental and thermal (TG and DTA) analyses, IR, UV-vis and 1H NMR spectra as well as magnetic moment. Mononuclear complexes are obtained with 1:1 molar ratio except [Mn(HOS) 2(H 2O) 2] and [Co(OS) 2](H 2O) 2 complexes which are obtained with 1:2 molar ratios. The IR spectra of ligand and metal complexes reveal various modes of chelation. The ligand behaves as a monobasic bidentate one and coordination occurs via the enolic oxygen atom and azomethine nitrogen atom. The ligand behaves also as a monobasic tridentate one and coordination occurs through the carbonyl oxygen atom, azomethine nitrogen atom and the hydroxyl oxygen. Moreover, the ligand behaves as a dibasic tridentate and coordination occurs via the enolic oxygen, azomethine nitrogen and the hydroxyl oxygen atoms. The electronic spectra and magnetic moment measurements reveal that all complexes possess octahedral geometry except the copper complexes possesses a square planar geometry. From the modeling studies, the bond length, bond angle, HOMO, LUMO and dipole moment had been calculated to confirm the geometry of the ligands and their investigated complexes. The thermal studies showed the type of water molecules involved in metal complexes as well as the thermal decomposition of some metal complexes. The protonation constant of the ligand and the stability constant of metal complexes were determined pH-metrically in 50% (v/v) dioxane-water mixture at 298 K and found to be consistent with Irving-Williams order. Moreover, the minimal inhibitory concentration (MIC) of these compounds against Staphylococcus aureus, Escherechia coli and Candida albicans were determined.

  3. Synthesis, structure and DFT study of cymantrenyl Fischer carbene complexes of group VI and VII transition metals

    NASA Astrophysics Data System (ADS)

    Fraser, Roan; van Rooyen, Petrus H.; Landman, Marilé

    2016-02-01

    Bi- and trimetallic carbene complexes of group VI and VII transition metals (Cr, Mo, W, Mn and Re), with CpMn(CO)3 as the initial synthon, have been synthesised according to the classical Fischer methodology. Crystal structures of the novel carbene complexes with general formula [Mx(CO)y-1{C(OEt)(MnCp(CO)3)}], where x = 1 then y = 3 or 6; x = 2 then y = 10, of the complexes are reported. A density functional theory (DFT) study was undertaken to determine natural bonding orbitals (NBOs) and conformational as well as isomeric aspects of the polymetallic complexes. Application of the second-order perturbation theory (SOPT) of the natural bond orbital (NBO) method revealed stabilizing interactions between the methylene C-H bonds and the carbonyl ligands of the carbene metal moiety. These stabilization interactions show a linear decrease for the group VI metal carbene complexes down the group.

  4. Alkene epoxidation employing metal nitro complexes

    DOEpatents

    Andrews, M.A.; Cheng, C.W.; Kelley, K.P.

    1982-07-15

    Process for converting alkenes to form epoxides utilizes transition metal nitro complexes of the formula: M(RCN)/sub 2/XNO/sub 2/ wherein M is palladium or platinum, R is an alkyl or aryl group containing up to 12 carbon atoms, and X is a monoanionic, monodentate ligand such as chlorine, optionally in the presence of molecular oxygen.

  5. Femtosecond Time-Resolved Infrared Spectra of Organometallic Complexes Bound to a Dinuclear Metal Center

    NASA Astrophysics Data System (ADS)

    Brown-Xu, Samantha E.; Durr, Christopher B.

    2012-06-01

    Compounds of the form M2L2L'2, where M2 is a quadruply bonded metal center (M = Mo or W) and L and L' are conjugated organic ligands, are known to show interesting photophysical properties and exhibit intense metal-to-ligand charge transfer (MLCT) transitions throughout the visible spectrum. Recently, we have modified one of the ligands to incorporate a transition metal carbonyl complex bound to an organic moiety. Following excitation into the MLCT band, the vibrational modes of the organometallic ligand can be observed by fs time-resolved infrared (TRIR) spectroscopy. This allows for a visualization of where the electron density resides in the excited states, which provides useful information for designing new materials that could later be incorporated into solar devices.

  6. Probing the microhydration of metal carbonyls: a photoelectron velocity-map imaging spectroscopic and theoretical study of Ni(CO)3(H2O)n().

    PubMed

    Xie, Hua; Zou, Jinghan; Kong, Xiangtao; Zhang, Weiqing; Ahmed, Musahid; Jiang, Ling

    2016-09-29

    A series of microhydrated nickel carbonyls, Ni(CO)3(H2O)n(-) (n = 0-4), are prepared via a laser vaporization supersonic cluster source in the gas phase and identified by mass-selected photoelectron velocity-map imaging spectroscopy and quantum chemical calculations. Vertical detachment energies for the n = 1-4 anions are measured from the photoelectron spectra to be 1.429 ± 0.103, 1.698 ± 0.090, 1.887 ± 0.080, and 2.023 ± 0.074 eV, respectively. The C-O stretching vibrational frequencies in the corresponding neutral clusters are determined to be 1968, 1950, 1945, and 1940 cm(-1) for n = 1-4, respectively, which are characteristic of terminal CO. It is determined that the hydrogen atom of the first water molecule is bound to the nickel center. Addition of a second water molecule prefers solvation at the carbonyl terminal. Spectroscopy combined with theory suggests that the solvation of nickel tricarbonyl is dominated by a water-ring network. The present findings would have important implications for the fundamental understanding of the multifaceted mechanisms of the multibody interaction of water and carbon monoxide with transition metals.

  7. Hydrogen bonding to carbonyl hydride complex Cp*Mo(PMe(3))(2)(CO)H and its role in proton transfer.

    PubMed

    Dub, Pavel A; Filippov, Oleg A; Belkova, Natalia V; Daran, Jean-Claude; Epstein, Lina M; Poli, Rinaldo; Shubina, Elena S

    2010-02-28

    The interaction of the carbonyl hydride complex Cp*Mo(PMe(3))(2)(CO)H with Brønsted (fluorinated alcohols, (CF(3))(n)CH(3-n)OH (n = 1-3), and CF(3)COOH) and Lewis (Hg(C(6)F(5))(2), BF(3).OEt(2)) acids was studied by variable temperature IR and NMR ((1)H, (31)P, (13)C) spectroscopies in combination with DFT/B3LYP calculations. Among the two functionalities potentially capable of the interaction - carbonyl and hydride ligands - the first was found to be the preferential binding site for weak acids, yielding CO...HOR or CO...Hg complexes as well as CO...(HOR)(2) adducts. For stronger proton donors ((CF(3))(3)COH, CF(3)COOH) hydrogen-bonding to the hydride ligand can be revealed as an intermediate of the proton transfer reaction. Whereas proton transfer to the CO ligand is not feasible, protonation of the hydride ligand yields an (eta(2)-H(2)) complex. Above 230 K dihydrogen evolution is observed leading to decomposition. Among the decomposition products compound [Cp*Mo(PMe(3))(3)(CO)](+)[(CF(3))(3)CO.2HOC(CF(3))(3)](-) resulting from a phosphine transfer reaction was characterized by X-ray diffraction. Reaction with BF(3).OEt(2) was found to produce [Cp*Mo(PMe(3))(2)(CO)BF(4)] via initial attack of the hydride ligand.

  8. Transition metal complexes supported by a neutral tetraamine ligand containing N,N-dimethylaniline units.

    PubMed

    Chu, Lei; Hardcastle, Kenneth I; MacBeth, Cora E

    2010-08-16

    First-row transition metal-halide complexes of tris(2-dimethylaminophenyl)amine, L(Me), have been synthesized and characterized. X-ray crystallographic studies on [Co(L(Me))Br]BPh(4), [Ni(L(Me))Cl]BPh(4), [Fe(L(Me))Cl]BPh(4), and [Cu(L(Me))Cl]BF(4) have been performed, and in all cases the ligand produces five-coordinate complexes with distorted trigonal bipyramidal coordination geometries. Where possible, comparisons have been made to the structures of related neutral tripodal ligands. Spectroscopic and magnetic studies of these complexes are also described. The Cu(I)-carbonyl complexes [Cu(L(Me))(CO)]PF(6) and [Cu(Me(6)tren)(CO)]PF(6) (Me(6)tren = tris(N,N-dimethylaminoethyl)amine) have also been prepared. Infrared spectroscopic investigations of these carbonyl complexes confirm that L(Me) is a less electron donating ligand than Me(6)tren and indicate that L(Me) can impart a different coordination number in the solid-state.

  9. Anharmonic Vibrational Spectroscopy on Metal Transition Complexes

    NASA Astrophysics Data System (ADS)

    Latouche, Camille; Bloino, Julien; Barone, Vincenzo

    2014-06-01

    Advances in hardware performance and the availability of efficient and reliable computational models have made possible the application of computational spectroscopy to ever larger molecular systems. The systematic interpretation of experimental data and the full characterization of complex molecules can then be facilitated. Focusing on vibrational spectroscopy, several approaches have been proposed to simulate spectra beyond the double harmonic approximation, so that more details become available. However, a routine use of such tools requires the preliminary definition of a valid protocol with the most appropriate combination of electronic structure and nuclear calculation models. Several benchmark of anharmonic calculations frequency have been realized on organic molecules. Nevertheless, benchmarks of organometallics or inorganic metal complexes at this level are strongly lacking despite the interest of these systems due to their strong emission and vibrational properties. Herein we report the benchmark study realized with anharmonic calculations on simple metal complexes, along with some pilot applications on systems of direct technological or biological interest.

  10. Infrared Multiple-Photon Dissociation spectroscopy of group II metal complexes with salicylate

    SciTech Connect

    Ryan P. Dain; Gary Gresham; Gary S. Groenewold; Jeffrey D. Steill; Jos Oomens; Michael J. van Stipdonk

    2011-07-01

    Ion-trap tandem mass spectrometry with collision-induced dissociation, and the combination of infrared multiple-photon dissociation (IRMPD) spectroscopy and density functional theory (DFT) calculations were used to characterize singly-charged, 1:1 complexes of Ca2+, Sr2+ and Ba2+ with salicylate. For each metal-salicylate complex, the CID pathways are: (a) elimination of CO2 and (b) formation of [MOH]+ where M=Ca2+, Sr2+ or Ba2+. DFT calculations predict three minima for the cation-salicylate complexes which differ in the mode of metal binding. In the first, the metal ion is coordinated by O atoms of the (neutral) phenol and carboxylate groups of salicylate. In the second, the cation is coordinated by phenoxide and (neutral) carboxylic acid groups. The third mode involves coordination by the carboxylate group alone. The infrared spectrum for the metal-salicylate complexes contains a number of absorptions between 1000 – 1650 cm-1, and the best correlation between theoretical and experimental spectra for the structure that features coordination of the metal ion by phenoxide and the carbonyl group of the carboxylic acid group, consistent with calculated energies for the respective species.

  11. Photoactivatable metal complexes: from theory to applications in biotechnology and medicine.

    PubMed

    Smith, Nichola A; Sadler, Peter J

    2013-07-28

    This short review highlights some of the exciting new experimental and theoretical developments in the field of photoactivatable metal complexes and their applications in biotechnology and medicine. The examples chosen are based on some of the presentations at the Royal Society Discussion Meeting in June 2012, many of which are featured in more detail in other articles in this issue. This is a young field. Even the photochemistry of well-known systems such as metal-carbonyl complexes is still being elucidated. Striking are the recent developments in theory and computation (e.g. time-dependent density functional theory) and in ultrafast-pulsed radiation techniques which allow photochemical reactions to be followed and their mechanisms to be revealed on picosecond/nanosecond time scales. Not only do some metal complexes (e.g. those of Ru and Ir) possess favourable emission properties which allow functional imaging of cells and tissues (e.g. DNA interactions), but metal complexes can also provide spatially controlled photorelease of bioactive small molecules (e.g. CO and NO)--a novel strategy for site-directed therapy. This extends to cancer therapy, where metal-based precursors offer the prospect of generating excited-state drugs with new mechanisms of action that complement and augment those of current organic photosensitizers.

  12. Pesticides Curbing Soil Fertility: Effect of Complexation of Free Metal Ions.

    PubMed

    Kaur, Sukhmanpreet; Kumar, Vijay; Chawla, Mohit; Cavallo, Luigi; Poater, Albert; Upadhyay, Niraj

    2017-01-01

    Researchers have suggested that the reason behind infertility is pernicious effect of broad spectrum pesticides on non target, beneficial microorganism of soil. Here, studying the chelating effect of selective organophosphate and carbamate pesticides with essential metal ions, at all possible combinations of three different pH (4 ± 0.05, 7 ± 0.05 and 9 ± 0.05) and three different temperatures (15 ± 0.5°C, 30 ± 0.5°C and 45 ± 0.5°C), shows very fast rate of reaction which further increases with increase of pH and temperature. Carbonyl oxygen of carbamate and phosphate oxygen of organophosphate were found to be common ligating sites among all the complexes. Formed metal complexes were found to be highly stable and water insoluble on interaction with essential metal ions in solvent medium as well as over silica. Density functional theory (DFT) calculations not only reinforced the experimental observations, but, after a wide computational conformational analysis, unraveled the nature of the high stable undesired species that consist of pesticides complexed by metal ions from the soil. All in all, apart from the direct toxicity of pesticides, the indirect effect by means of complexation of free metal ions impoverishes the soil.

  13. Synthesis, thermal and spectroscopic behaviors of metal-drug complexes: La(III), Ce(III), Sm(III) and Y(III) amoxicillin trihydrate antibiotic drug complexes.

    PubMed

    Refat, Moamen S; Al-Maydama, Hussein M A; Al-Azab, Fathi M; Amin, Ragab R; Jamil, Yasmin M S

    2014-07-15

    The metal complexes of Amoxicillin trihydrate with La(III), Ce(III), Sm(III) and Y(III) are synthesized with 1:1 (metal:Amox) molar ratio. The suggested formula structures of the complexes are based on the results of the elemental analyses, molar conductivity, (infrared, UV-visible and fluorescence) spectra, effective magnetic moment in Bohr magnetons, as well as the thermal analysis (TG), and characterized by X-ray powder diffraction (XRD) and scanning electron microscopy (SEM). The results obtained suggested that Amoxicillin reacted with metal ions as tridentate ligands, coordinating the metal ion through its amino, imino, and β-lactamic carbonyl. The kinetic thermodynamic parameters such as: Ea, ΔH(*), ΔS(*) and ΔG(*) were estimated from the DTG curves.

  14. Ruthenium(II) carbonyl complexes bearing CCC-pincer bis-(carbene) ligands: synthesis, structures and activities toward recycle transfer hydrogenation reactions.

    PubMed

    Naziruddin, Abbas Raja; Huang, Zhao-Jiunn; Lai, Wei-Chih; Lin, Wan-Jung; Hwang, Wen-Shu

    2013-09-28

    A new series of ruthenium(II) carbonyl complexes with benzene-based CCC-pincer bis-(carbene) ligands, [((R)CCC(R))Ru(CO)2(X)](0/+) and [((R)CCC(R))Ru(CO)(NN)](+) ((R)CCC(R) = 2,6-bis-(1-alkylimidazolylidene)benzene, R = Me or (n)Bu; X = I, Br, CH3CN, or 6-(aminomethyl)pyridine (ampy); NN = 2·CH3CN, or chelating ampy or bipyridine), was synthesized and fully characterized. X-Ray structure determinations revealed that these eight complexes have pseudo-octahedral configurations around the ruthenium center with the pincer ligand occupying three meridional sites. These complexes prove to be efficient precatalysts demonstrating very good activity and reusability for the transfer hydrogenation of ketones.

  15. Use of ionic liquids (ILs) for the IL-anion size-dependent formation of Cr, Mo and W nanoparticles from metal carbonyl M(CO)6 precursors.

    PubMed

    Redel, Engelbert; Thomann, Ralf; Janiak, Christoph

    2008-04-21

    Stable chromium, molybdenum and tungsten nanoparticles are obtained reproducibly by thermal or photolytic decomposition under argon from mononuclear metal carbonyl precursors M(CO)(6) (M=Cr, Mo, W) suspended in the ionic liquids BMim(+)BF(4)(-), BMim(+)OTf(-) and BtMA(+)Tf(2)N(-) (BMim(+)=n-butyl-methyl-imidazolium, BtMA(+)=n-butyl-trimethyl-ammonium, Tf(2)N=N(O(2)SCF(3))(2), OTf=O(3)SCF(3)) with a very small and uniform size of 1 to 1.5 nm in BMim(+)BF(4)(-) which increases with the molecular volume of the ionic liquid anion to approximately 100 nm in BtMA(+)Tf(2)N(-) [characterization by transmission electron microscopy (TEM), dynamic light scattering and transmission electron diffraction (TED) analysis].

  16. Luminescent Triphosphine Cyanide d(10) Metal Complexes.

    PubMed

    Chakkaradhari, Gomathy; Chen, Yi-Ting; Karttunen, Antti J; Dau, Minh Thuy; Jänis, Janne; Tunik, Sergey P; Chou, Pi-Tai; Ho, Mei-Lin; Koshevoy, Igor O

    2016-03-07

    Coinage metal cyanides efficiently react with a triphosphine. PPh2C6H4-PPh-C6H4PPh2 (P(3)). to give the complexes M(P(3))CN, where M = Cu (1), Ag (2), and Au (3), which can further interact with coordinatively unsaturated metal centers [M(P(3))](+) to give the homobimetallic [(P(3))M-CN-M(P(3))](+)X(-) [M = Cu (4a with X(-) = CF3SO3(-) and 4b with X(-) = BF4(-)), Ag (5)] or heterometallic [(P(3))Au-CN-Ag(P(3))](+) (6) species. Extension of this approach also provided the trinuclear complex [(P(3))Cu-NC-Au-CN-Cu(P(3))](+) (7). Compounds 1-5 were characterized in the solid state by X-ray crystallography. The NMR spectroscopic studies revealed that all of the complexes except 6 retain their structures in solution. The title compounds are luminescent in the solid state, with quantum yields ranging from 8 to 87%. The observed photoemission originates mainly from the metal-to-ligand charge-transfer states according to time-dependent density functional theory computational studies. The crystalline bimetallic Cu complexes 4a/4b demonstrate extremely high sensitivity of the emission intensity to molecular O2 (KSV1 = 639 atm(-1) and LOD = 0.010% for 3 times the signal-to-noise ratio).

  17. Matrix isolation and ESR study of unstable intermediate generated by radiation techniques from metal carbonyl complexes

    NASA Astrophysics Data System (ADS)

    Buttafava, A.; Faucitano, A.; Martinotti, F.

    Exposure of MeTHF solutions of M(CO) 6 (M=Cr, Mo, W) to γ-rays or photoionization with TMPD at 77 K gives paramagnetic species attributed to 17 electron radical anions M(CO) overlineṡ. The excess energy arising from the primary electron capture process is responsible of the fast M—CO bond breaking which prevents the trapping of 19-electron species M(CO) overlineṡ. Experimental and EHT-MO calculated g-tensors of the pentacoordinated anions are consistent with a square pyramidal C4ν structure having the unpaired electron in a molecular orbital with a high dz2 character.

  18. Metal-Metal Bonding in Uranium-Group 10 Complexes.

    PubMed

    Hlina, Johann A; Pankhurst, James R; Kaltsoyannis, Nikolas; Arnold, Polly L

    2016-03-16

    Heterobimetallic complexes containing short uranium-group 10 metal bonds have been prepared from monometallic IU(IV)(OAr(P)-κ(2)O,P)3 (2) {[Ar(P)O](-) = 2-tert-butyl-4-methyl-6-(diphenylphosphino)phenolate}. The U-M bond in IU(IV)(μ-OAr(P)-1κ(1)O,2κ(1)P)3M(0), M = Ni (3-Ni), Pd (3-Pd), and Pt (3-Pt), has been investigated by experimental and DFT computational methods. Comparisons of 3-Ni with two further U-Ni complexes XU(IV)(μ-OAr(P)-1κ(1)O,2κ(1)P)3Ni(0), X = Me3SiO (4) and F (5), was also possible via iodide substitution. All complexes were characterized by variable-temperature NMR spectroscopy, electrochemistry, and single crystal X-ray diffraction. The U-M bonds are significantly shorter than any other crystallographically characterized d-f-block bimetallic, even though the ligand flexes to allow a variable U-M separation. Excellent agreement is found between the experimental and computed structures for 3-Ni and 3-Pd. Natural population analysis and natural localized molecular orbital (NLMO) compositions indicate that U employs both 5f and 6d orbitals in covalent bonding to a significant extent. Quantum theory of atoms-in-molecules analysis reveals U-M bond critical point properties typical of metallic bonding and a larger delocalization index (bond order) for the less polar U-Ni bond than U-Pd. Electrochemical studies agree with the computational analyses and the X-ray structural data for the U-X adducts 3-Ni, 4, and 5. The data show a trend in uranium-metal bond strength that decreases from 3-Ni down to 3-Pt and suggest that exchanging the iodide for a fluoride strengthens the metal-metal bond. Despite short U-TM (transition metal) distances, four other computational approaches also suggest low U-TM bond orders, reflecting highly transition metal localized valence NLMOs. These are more so for 3-Pd than 3-Ni, consistent with slightly larger U-TM bond orders in the latter. Computational studies of the model systems (PH3)3MU(OH)3I (M = Ni, Pd) reveal

  19. Synthesis, characterization, redox property and biological activity of Ru(II) carbonyl complexes containing O,N-donor ligands and heterocyclic bases

    NASA Astrophysics Data System (ADS)

    Kumar, K. Naresh; Ramesh, R.

    2004-10-01

    Stable ruthenium(II) carbonyl complexes having the general composition [RuCl(CO)(PPh 3)(B)(L)] (where B=PPh 3, pyridine, piperidine or morpholine; L = anion of bidentate Schiff bases (Vanmet, Vanampy, Vanchx)) were synthesized from the reaction of [RuHCl(CO)(PPh 3) 2(B)] with bidentate Schiff base ligands derived from condensation of o-vanillin with primary amines such as methylamine, 2-aminopyridine and cyclohexylamine. The new complexes were characterized by elemental analysis, IR, UV-Vis and 1H NMR spectral data. The redox property of the complexes were studied by cyclic voltammetric technique and the stability of the complexes towards oxidation were related to the electron releasing or electron withdrawing ability of the substituent in the phenyl ring of o-vanillin. An octahedral geometry has been assigned for all the complexes. In all the above reactions, the Schiff bases replace one molecule of PPh 3 and hydride ion from the starting complexes, which indicate that the Ru-N bonds present in the complexes containing heterocyclic nitrogen bases are stronger than the Ru-P. The Schiff bases and their ruthenium(II) complexes have been tested in vitro to evaluate their activity against bacteria, viz., Staphylococus aureus (209p) and E. coli (ESS 2231).

  20. Photoactivatable metal complexes: from theory to applications in biotechnology and medicine

    PubMed Central

    Smith, Nichola A.; Sadler, Peter J.

    2013-01-01

    This short review highlights some of the exciting new experimental and theoretical developments in the field of photoactivatable metal complexes and their applications in biotechnology and medicine. The examples chosen are based on some of the presentations at the Royal Society Discussion Meeting in June 2012, many of which are featured in more detail in other articles in this issue. This is a young field. Even the photochemistry of well-known systems such as metal–carbonyl complexes is still being elucidated. Striking are the recent developments in theory and computation (e.g. time-dependent density functional theory) and in ultrafast-pulsed radiation techniques which allow photochemical reactions to be followed and their mechanisms to be revealed on picosecond/nanosecond time scales. Not only do some metal complexes (e.g. those of Ru and Ir) possess favourable emission properties which allow functional imaging of cells and tissues (e.g. DNA interactions), but metal complexes can also provide spatially controlled photorelease of bioactive small molecules (e.g. CO and NO)—a novel strategy for site-directed therapy. This extends to cancer therapy, where metal-based precursors offer the prospect of generating excited-state drugs with new mechanisms of action that complement and augment those of current organic photosensitizers. PMID:23776303

  1. Electronic states of alkali metal-NTCDA complexes: A DFT study

    NASA Astrophysics Data System (ADS)

    Tachikawa, Hiroto; Kawabata, Hiroshi

    2015-10-01

    Structures and electronic states of organic-inorganic compound of 1,4,5,8-naphthalene-tetracarboxylic-dianhydride (NTCDA) with alkali metals, Mn(NTCDA) (Mdbnd Li and Na, n = 0-2), have been investigated by means of hybrid density functional theory (DFT) calculations. From the DFT calculations, it was found that the electronic state of the complex at the ground state is characterized by a charge-transfer state expressed by (M)+(NTCDA)-. The alkali metals were bound equivalently to the carbonyl oxygen and ether oxygen atoms of NTCDA. The Cdbnd O double bond character of NTCDA was changed to a C-O single bond like character by the strong interaction of M to the Cdbnd O and O sites. This change was the origin of the red-shift of the IR spectrum. The UV-vis absorption spectra of Mn(NTCDA) were theoretically predicted on the basis of theoretical results.

  2. Synthesis, characterization, biological activity, molecular modeling and docking studies of complexes 4-(4-hydroxy)-3-(2-pyrazine-2-carbonyl)hydrazonomethylphenyl-diazen-yl-benzenesulfonamide with manganese(II), cobalt(II), nickel(II), zinc(II) and cadmium(II)

    NASA Astrophysics Data System (ADS)

    Alaghaz, Abdel-Nasser M. A.; Zayed, Mohamed E.; Alharbi, Suliman A.; Ammar, Reda A. A.; Elhenawy, Ahmed

    2015-03-01

    A new series of complexes of 4-(4-hydroxy)-3-(2-pyrazine-2-carbonyl)hydrazonomethylphenyl-diazen-yl-benzenesulfonamide (HL) with Mn(II), Co(II), Ni(II), Zn(II) and Cd(II) have been prepared and characterized by different physical techniques. The IR spectra of the prepared complexes were suggested that the ligand behaves as a tri-dentate ligand through the carbonyl oxygen, azomethine nitrogen and phenolic oxygen atoms (ONO). Electronic spectra and magnetic susceptibility measurements reveal octahedral geometry for all complexes. The elemental analyses and mass spectral data have justified the ML2 composition of complexes. The EPR spectra of Mn(II), Co(II) and Ni(II) complexes support the mononuclear structure. The crystal field splitting, Racah repulsion and nephelauxetic parameters and determined from the electronic spectra of the complexes. Thermal properties and decomposition kinetics of all complexes are investigated. The geometry of the metal complexes has been optimized with the help of molecular modeling. The biological activity of these compounds against various fungi has been investigated.

  3. Ultrahigh-field NMR spectroscopy of quadrupolar transition metals: 55Mn NMR of several solid manganese carbonyls.

    PubMed

    Ooms, Kristopher J; Feindel, Kirk W; Terskikh, Victor V; Wasylishen, Roderick E

    2006-10-16

    55Mn NMR spectra acquired at 21.14 T (nu(L)(55Mn) = 223.1 MHz) are presented and demonstrate the advantages of using ultrahigh magnetic fields for characterizing the chemical shift tensors of several manganese carbonyls: eta5-CpMn(CO)3, Mn2(CO)10, and (CO)5MnMPh3 (M = Ge, Sn, Pb). For the compounds investigated, the anisotropies of the manganese chemical shift tensors are less than 250 ppm except for eta5-CpMn(CO)3, which has an anisotropy of 920 ppm. At 21.14 T, one can excite the entire m(I) = 1/2 <--> m(I) = -1/2 central transition of eta5-CpMn(CO)3, which has a breadth of approximately 700 kHz. The breadth arises from second-order quadrupolar broadening due to the 55Mn quadrupolar coupling constant of 64.3 MHz, as well as the anisotropic shielding. Subtle variations in the electric field gradient tensors at the manganese are observed for crystallographically unique sites in two of the solid pentacarbonyls, resulting in measurably different C(Q) values. MQMAS experiments are able to distinguish four magnetically unique Mn sites in (CO)(5)MnPbPh3, each with slightly different values of delta(iso), C(Q), and eta(Q).

  4. Ultrafast photophysics of transition metal complexes.

    PubMed

    Chergui, Majed

    2015-03-17

    The properties of transition metal complexes are interesting not only for their potential applications in solar energy conversion, OLEDs, molecular electronics, biology, photochemistry, etc. but also for their fascinating photophysical properties that call for a rethinking of fundamental concepts. With the advent of ultrafast spectroscopy over 25 years ago and, more particularly, with improvements in the past 10-15 years, a new area of study was opened that has led to insightful observations of the intramolecular relaxation processes such as internal conversion (IC), intersystem crossing (ISC), and intramolecular vibrational redistribution (IVR). Indeed, ultrafast optical spectroscopic tools, such as fluorescence up-conversion, show that in many cases, intramolecular relaxation processes can be extremely fast and even shorter than time scales of vibrations. In addition, more and more examples are appearing showing that ultrafast ISC rates do not scale with the magnitude of the metal spin-orbit coupling constant, that is, that there is no heavy-atom effect on ultrafast time scales. It appears that the structural dynamics of the system and the density of states play a crucial role therein. While optical spectroscopy delivers an insightful picture of electronic relaxation processes involving valence orbitals, the photophysics of metal complexes involves excitations that may be centered on the metal (called metal-centered or MC) or the ligand (called ligand-centered or LC) or involve a transition from one to the other or vice versa (called MLCT or LMCT). These excitations call for an element-specific probe of the photophysics, which is achieved by X-ray absorption spectroscopy. In this case, transitions from core orbitals to valence orbitals or higher allow probing the electronic structure changes induced by the optical excitation of the valence orbitals, while also delivering information about the geometrical rearrangement of the neighbor atoms around the atom of

  5. 40 CFR 721.4596 - Diazo substituted carbomonocyclic metal complex.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... metal complex. 721.4596 Section 721.4596 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.4596 Diazo substituted carbomonocyclic metal complex. (a) Chemical... as a diazo substituted carbomonocyclic metal complex (PMN P-94-1039) is subject to reporting...

  6. 40 CFR 721.4596 - Diazo substituted carbomonocyclic metal complex.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... metal complex. 721.4596 Section 721.4596 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.4596 Diazo substituted carbomonocyclic metal complex. (a) Chemical... as a diazo substituted carbomonocyclic metal complex (PMN P-94-1039) is subject to reporting...

  7. 40 CFR 721.10104 - Halophosphate mixed metal complex (generic).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Halophosphate mixed metal complex... Specific Chemical Substances § 721.10104 Halophosphate mixed metal complex (generic). (a) Chemical... as halophosphate mixed metal complex (PMN P-04-254) is subject to reporting under this section...

  8. 40 CFR 721.4596 - Diazo substituted carbomonocyclic metal complex.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... metal complex. 721.4596 Section 721.4596 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.4596 Diazo substituted carbomonocyclic metal complex. (a) Chemical... as a diazo substituted carbomonocyclic metal complex (PMN P-94-1039) is subject to reporting...

  9. 40 CFR 721.10104 - Halophosphate mixed metal complex (generic).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Halophosphate mixed metal complex... Specific Chemical Substances § 721.10104 Halophosphate mixed metal complex (generic). (a) Chemical... as halophosphate mixed metal complex (PMN P-04-254) is subject to reporting under this section...

  10. 40 CFR 721.10104 - Halophosphate mixed metal complex (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Halophosphate mixed metal complex... Specific Chemical Substances § 721.10104 Halophosphate mixed metal complex (generic). (a) Chemical... as halophosphate mixed metal complex (PMN P-04-254) is subject to reporting under this section...

  11. 40 CFR 721.10104 - Halophosphate mixed metal complex (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Halophosphate mixed metal complex... Specific Chemical Substances § 721.10104 Halophosphate mixed metal complex (generic). (a) Chemical... as halophosphate mixed metal complex (PMN P-04-254) is subject to reporting under this section...

  12. 40 CFR 721.10104 - Halophosphate mixed metal complex (generic).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Halophosphate mixed metal complex... Specific Chemical Substances § 721.10104 Halophosphate mixed metal complex (generic). (a) Chemical... as halophosphate mixed metal complex (PMN P-04-254) is subject to reporting under this section...

  13. 40 CFR 721.4596 - Diazo substituted carbomonocyclic metal complex.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... metal complex. 721.4596 Section 721.4596 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.4596 Diazo substituted carbomonocyclic metal complex. (a) Chemical... as a diazo substituted carbomonocyclic metal complex (PMN P-94-1039) is subject to reporting...

  14. 40 CFR 721.4596 - Diazo substituted carbomonocyclic metal complex.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... metal complex. 721.4596 Section 721.4596 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.4596 Diazo substituted carbomonocyclic metal complex. (a) Chemical... as a diazo substituted carbomonocyclic metal complex (PMN P-94-1039) is subject to reporting...

  15. Re(I) carbonyl complexes of N-[(2-pyridyl)methyliden]-α (or β)-aminonaphthalene: Synthesis, structure, electrochemistry and DFT analysis

    NASA Astrophysics Data System (ADS)

    Pramanik, Ajoy Kumar; Jana, Mahendra Sekhar; Kundu, Subhankar; Mondal, Tapan Kumar

    2012-06-01

    The article deals with a combined experimental and computational study of rhenium tricarbonyl Schiff base complexes having general formula fac-[ReCl(CO)3(L1/L2)] (1/2) (L1 = N-[(2-pyridyl)methyliden]-α-aminonaphthalene and L2 = N-[(2-pyridyl)methyliden]-β-aminonaphthalene). The complexes fac-[ReCl(CO)3(L1/L2)] (1/2) have been synthesized and characterized by elemental analysis, spectroscopic studies, electrochemistry and X-ray crystal analysis for complex 2. Crystal structure of 2 reveals the facial geometry of the carbonyl ligand and Re is in distorted octahedral environment in the complex. The electronic structure, redox properties, absorption and emission properties have been explained based on DFT and TDDFT calculations. The complexes show MLCT bands at 395-405 nm and emitted at 425-435 nm upon excitation at 310 nm, characterized as ILCT transitions. The complexes exhibit two irreversible ReII/ReI and ReIII/ReII oxidative responses when scanned in the potential range 0.0-2.0 V in cyclic voltammetric studies.

  16. Analysis of metal-EDTA complexes by electrospray mass spectrometry

    SciTech Connect

    Baron, D.; Hering, J.G.

    1998-07-01

    Solutions of the strong complexing agent ethylenediaminetetraacetic acid (EDTA) and Cu, Pb, Cd, Al, and Fe(III) were examined by electrospray mass spectrometry (ES/MS). Uncomplexed EDTA and metal-EDTA complexes survive the electrospray process intact and can be detected simultaneously by mass spectrometry. Best sensitivity was achieved in the positive ion mode in which EDTA and EDTA-metal complexes (present in solution as anions) were detected as protonated species with a single positive charge. Except for the protonation, the aqueous metal-EDTA complexes are preserved and neither fragmentation of complexes nor formation of clusters with more than one metal or ligand were observed in the mass spectra. Detection limits are between approximately 1 to 2 {micro}M for uncomplexed EDTA and for the Cu-EDTA and Pb-EDTA complexes, with a linear range up to 10{sup {minus}4} M. Calibrations based on solutions with equimolar concentrations of EDTA and Cu or Pb can be used to quantify EDTA-metal complexes in solutions with excess EDTA or metal, and in solutions with more than one metal present. Isotopic signatures of metals in the metal-ligand complexes are preserved, allowing the identification of the metal in a metal-ligand complex. Isotopic signatures of metals can therefore aid in the identification of metal-ligand complexes in unknown samples.

  17. Structures, Interconversions, and Spectroscopy of Iron Carbonyl Clusters with an Interstitial Carbide: Localized Metal Center Reduction by Overall Cluster Oxidation.

    PubMed

    Kuppuswamy, Subramaniam; Wofford, Joshua D; Joseph, Chris; Xie, Zhu-Lin; Ali, Azim K; Lynch, Vincent M; Lindahl, Paul A; Rose, Michael J

    2017-05-15

    The syntheses, interconversions, and spectroscopic properties of a set of iron carbonyl clusters containing an interstitial carbide are reported. This includes the low temperature X-ray structures of the six-iron clusters (Y)2[Fe6(μ6-C)(μ2-CO)4(CO)12] (1a-c; where Y = NMe4, NEt4, PPh4); the five-iron cluster [Fe5(μ5-C)(CO)15] (3); and the novel formulation of the five-iron cluster (NMe4)2[Fe5(μ5-C)(μ2-CO)(CO)13] (4). Also included in this set is the novel charge-neutral cluster, [Fe6(μ6-C)(CO)18] (2), for which we were unable to obtain a crystallographic structure. As synthetic proof for the identity of 2, we performed a closed loop of interconversions within a family of crystallographically defined species (1, 3, and 4): [Fe6](2-) → [Fe6](0) → [Fe5](0) → [Fe5](2-) → [Fe6](2-). The structural, spectroscopic, and electronic properties of this "missing link" cluster 2 were investigated by IR, Raman, XPS, and Mössbauer spectroscopies-as well as by DFT calculations. A single νCO feature (1965 cm(-1)) in the IR spectrum of 2, as well as a prominent Raman feature (νsymm = 1550 cm(-1)), are consistent with the presence of terminal carbonyls and a {(μ6-C)Fe6} arrangement of iron centers around the central carbide. The XPS of 2 exhibits a higher energy Fe 2p3/2 feature (707.4 eV) as compared to that of 1 (705.5 eV), consistent with the two-electron oxidation induced by treatment of 1 with two equivalents of [Fc](PF6) under CO atmosphere (for the two added CO ligands). DFT calculations indicate two axial and four equatorial Fe sites in 1, all of which have the same or similar oxidation states, for example, two Fe(0) and four Fe(+0.5). These assignments are supported by Mössbauer spectra for 1, which exhibit two closely spaced quadrupole doublets with δ = 0.076 and 0.064 mm s(-1). The high-field Mössbauer spectrum of 2 (4.2 K) exhibits three prominent quadrupole doublets with δ = -0.18, -0.11, and +0.41 mm s(-1). This indicates three pairs of chemically

  18. Transition Metal Complexes of Expanded Porphyrins

    PubMed Central

    Sessler, Jonathan L.; Tomat, Elisa

    2008-01-01

    Over the last two decades, the rapid development of new synthetic routes for the preparation of expanded porphyrin macrocycles has allowed exploration of a new frontier consisting of “porphyrin-like” coordination chemistry. In this Account, we summarize our exploratory forays into the still relatively poorly explored area of oligopyrrolic macrocycle metalation chemistry. Specifically, we describe our successful formation of both mono- and binuclear complexes and in doing so highlight the diversity of coordination modes available to expanded porphyrin-type ligands. The nature of the inserted cation, the emerging role of tautomeric equilibria, and the importance of hydrogen-bonding interactions in regulating this chemistry are also discussed. PMID:17397134

  19. Quantum chemical interpretation of ultrafast luminescence decay and intersystem crossings in rhenium(I) carbonyl bipyridine complexes.

    PubMed

    Gourlaouen, Christophe; Eng, Julien; Otsuka, Miho; Gindensperger, Etienne; Daniel, Chantal

    2015-01-13

    Ultrafast luminescence decay and intersystem crossing processes through the seven low-lying singlet and triplet excited states of [Re (X)(CO)3(bpy)] (X = Cl, Br, I; bpy = 2,2'-bipyridine) are interpreted on the basis of time-dependent density functional theory (TD-DFT) electronic structure calculations performed in acetonitrile and including spin-orbit coupling (SOC) effects within the zeroth-order approximation. It is shown that the red shift of the lowest part of the spectra by SOC increases from X = Cl (0.06 eV) to X = Br (0.09 eV) and X = I (0.18 eV) due to the participation of the triplet sublevels to the absorption. The six lowest "spin-orbit" states remain largely triplet in character and the maximum of absorption is not drastically affected by SOC. While the energy of the excited states is affected by SOC, the character of these states is not significantly modified: SOC mixes states of the same nature, namely metal-to-ligand-charge-transfer/halide-to-ligand-charge-transfer (MLCT/XLCT). This mixing can be large, however, as illustrated by the S1/T2 (a(1)A″/a(3)A') mixing that amounts to about 50:50 within the series Cl > Br > I. On the basis of the optimized structures of the six lowest excited states an interpretation of the emission signals detected by ultrafast luminescence spectroscopy is proposed. It is shown that whereas the experimental Stokes shift of 6000 cm(-1) observed for the three complexes is well reproduced without SOC correction for the Cl and Br complexes, SOC effects have to be taken into account for the iodide complex. The early signal of ultrafast luminescence detected immediately after absorption at 400 nm to the S2 state, covering the 500-550 nm energy domain and characterized by a decay τ1 = 85 fs (X = Cl) and 128 fs (X = Br), is attributed to S2 calculated at 505 and 522 nm, respectively, and to some extend to T3 by SOC. The intermediate band observed at longer time-scale between 550 and 600 nm with emissive decay time τ2 = 340 fs

  20. Isoniazid metal complex reactivity and insights for a novel anti-tuberculosis drug design.

    PubMed

    Sousa, Eduardo Henrique Silva; Basso, Luiz Augusto; Santos, Diógenes S; Diógenes, Izaura Cirino Nogueira; Longhinotti, Elisane; Lopes, Luiz Gonzaga de França; Moreira, Icaro de Sousa

    2012-02-01

    For over a decade, tuberculosis (TB) has been the leading cause of death among infectious diseases. Since the 1950s, isoniazid has been used as a front-line drug in the treatment of TB; however, resistant TB strains have limited its use. The major route of isoniazid resistance relies on KatG enzyme disruption, which does not promote an electron transfer reaction. Here, we investigated the reactivity of isoniazid metal complexes as prototypes for novel self-activating metallodrugs against TB with the aim to overcome resistance. Reactivity studies were conducted with hydrogen peroxide, hexacyanoferrate(III), and aquopentacyanoferrate(III). The latter species showed a preference for the inner-sphere electron transfer reaction pathway. Additionally, electron transfer reaction performed with either free isoniazid or (isoniazid)pentacyanoferrate(II) complex resulted in similar oxidized isoniazid derivatives as observed when the KatG enzyme was used. However, upon metal coordination, a significant enhancement in the formation of isonicotinic acid was observed compared with that of isonicotinamide. These results suggest that the pathway of a carbonyl-centered radical might be favored upon coordination to the Fe(II) owing to the π-back-bonding effect promoted by this metal center; therefore, the isoniazid metal complex could serve as a potential metallodrug. Enzymatic inhibition assays conducted with InhA showed that the cyanoferrate moiety is not the major player involved in this inhibition but the presence of isoniazid is required in this process. Other isoniazid metal complexes, [Ru(CN)(5)(izd)](3-) and [Ru(NH(3))(5)(izd)](2+) (where izd is isoniazid), were also unable to inhibit InhA, supporting our proposed self-activating mechanism of action. We propose that isoniazid reactivity can be rationally modulated by metal coordination chemistry, leading to the development of novel anti-TB metallodrugs.

  1. Cooperative Catalysis of Combined Systems of Transition-Metal Complexes with Lewis Acids: Theoretical Understanding.

    PubMed

    Guan, Wei; Zeng, Guixiang; Kameo, Hajime; Nakao, Yoshiaki; Sakaki, Shigeyoshi

    2016-10-01

    The combination of transition-metal complexes and Lewis acids has been recently applied to several catalytic reactions, in which the Lewis acid plays a crucial role as a non-innocent additive to accelerate the reaction. In this review article, the reasons for the acceleration by the Lewis acid are discussed based on our recent theoretical studies. In the H-H σ-bond activation of a dihydrogen molecule by a nickel(0)-borane complex, the empty p orbital of the borane moiety interacts with the H-H σ bonding MO to form charge transfer (CT) from the dihydrogen molecule to the borane moiety to accelerate the reaction. In the B-F σ-bond activation of BF3 by a platinum(0)-bisphosphine complex, the second BF3 molecule interacts with the F atom that is dissociating from the B atom to stabilize the transition state and product by the CT from the F atom to the second BF3 . In this reaction, the substrate BF3 plays a crucial role as the Lewis acid to accelerate the activation of the B-F σ bond. In the nickel-catalyzed decyanative coupling of arylcarboxybenzonitriles with acetylenes, two molecules of the aluminum Lewis acid interact with the cyano N atom and the carbonyl O atom of the substrate to stabilize the transition state and intermediate. In the nickel-catalyzed alkylation of aromatic amides with alkenes, the Lewis acid enhances the para regioselectivity of alkylation by interacting with the carbonyl O atom. In the nickel-catalyzed carboxylation of sp(3) carbon and sp carbon atoms with carbon dioxide, not the σ-bond activation but the insertion reaction of carbon dioxide into the metal-carbon bond is accelerated by the Lewis acid by interacting with the O atom of carbon dioxide, because the CT from the metal-carbon bond to carbon dioxide is enhanced by the interaction. This theoretical knowledge suggests that the combination of transition-metal complex and Lewis acid can broaden the application range of transition-metal complex as catalyst. © 2016 The Chemical

  2. Metal encapsulating carbon nanostructures from oligoalkyne metal complexes

    SciTech Connect

    Dosa, P.I.; Erben, C.; Iyer, V.S.; Vollhardt, K.P.C.; Wasser, I.M.

    1999-11-10

    Carbon nanotubes, onions, and related closed-shell carbon particles have commanded extensive recent attention because of their potential applications as unique electronic, magnetic, and mechanically robust materials. When filled with metals, such nanocapsules have additional promise as magnetic particles, contrasting agents, protecting cloaks, and catalysts and in other applications. Among the various methods for their preparation, the transition metal (especially Fe, Co, and Ni) catalyzed pyrolysis of small organic molecules has shown promise for larger scale production and in structural control. While the use of organometallic complexes as solid catalyst precursors or copyrolytic gaseous ingredients has been reported, all of these studies have been limited to gas-phase experiments at relatively high temperatures. There is very little literature that deals with the organic solid-state generation of carbon nanotubes. The latter suffers from extreme conditions, poor yields, or not readily modifiable starting materials. Development of synthetic organic approaches to closed shell large carbon structures is desirable but in its infancy. Here the authors present a significant step in its progress.

  3. Synthesis, characterization and antibacterial properties of some trivalent metal complexes with [(2-hydroxy-1-naphthaldehyde)-3-isatin]-bishydrazone.

    PubMed

    Murukan, Balakrishnan; Mohanan, Kochukittan

    2007-02-01

    Complexes of manganese(III), iron(III) and cobalt(III) with a bishydrazone, formed by condensation of isatin monohydrazone with 2-hydroxy-1-naphthaldehyde, have been synthesized. The spectral data reveal that the ligand acts as monobasic tridentate, coordinating through the deprotonated naphtholate oxygen, azomethine nitrogen, and carbonyl oxygen. Molar conductance values adequately support the electrolytic nature of the complexes. On the basis of the above observations the complexes have been formulated as [M(NIB)2]X where M = Mn(III), Fe(III) or Co(III); X = Cl-, NO3(-); or OAc-; HNIB = [(2-hydroxy-1-naphthaldehyde)-3-isatin]-bishydrazone. Based on electronic spectral data and magnetic moment values, an octahedral geometry has been proposed. The iron(III) complex has been subjected to thermal decomposition studies. The ligand and the metal complexes have been screened for their antibacterial activity and it has been observed that the complexes are more potent bactericides than the ligand.

  4. The Hydrolysis of Carbonyl Sulfide at Low Temperature: A Review

    PubMed Central

    Zhao, Shunzheng; Yi, Honghong; Tang, Xiaolong; Jiang, Shanxue; Gao, Fengyu; Zhang, Bowen; Zuo, Yanran; Wang, Zhixiang

    2013-01-01

    Catalytic hydrolysis technology of carbonyl sulfide (COS) at low temperature was reviewed, including the development of catalysts, reaction kinetics, and reaction mechanism of COS hydrolysis. It was indicated that the catalysts are mainly involved metal oxide and activated carbon. The active ingredients which can load on COS hydrolysis catalyst include alkali metal, alkaline earth metal, transition metal oxides, rare earth metal oxides, mixed metal oxides, and nanometal oxides. The catalytic hydrolysis of COS is a first-order reaction with respect to carbonyl sulfide, while the reaction order of water changes as the reaction conditions change. The controlling steps are also different because the reaction conditions such as concentration of carbonyl sulfide, reaction temperature, water-air ratio, and reaction atmosphere are different. The hydrolysis of carbonyl sulfide is base-catalyzed reaction, and the force of the base site has an important effect on the hydrolysis of carbonyl sulfide. PMID:23956697

  5. 40 CFR 721.4594 - Substituted azo metal complex dye.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Substituted azo metal complex dye. 721... Substances § 721.4594 Substituted azo metal complex dye. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as a substituted azo metal...

  6. 40 CFR 721.4594 - Substituted azo metal complex dye.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Substituted azo metal complex dye. 721... Substances § 721.4594 Substituted azo metal complex dye. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as a substituted azo metal...

  7. 40 CFR 721.4594 - Substituted azo metal complex dye.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Substituted azo metal complex dye. 721... Substances § 721.4594 Substituted azo metal complex dye. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as a substituted azo metal...

  8. 40 CFR 721.4594 - Substituted azo metal complex dye.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Substituted azo metal complex dye. 721... Substances § 721.4594 Substituted azo metal complex dye. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as a substituted azo metal...

  9. 40 CFR 721.4594 - Substituted azo metal complex dye.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Substituted azo metal complex dye. 721... Substances § 721.4594 Substituted azo metal complex dye. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as a substituted azo metal...

  10. Effects of Carbonyl Bond and Metal Cluster Dissociation and Evaporation Rates on Predictions of Nanotube Production in HiPco

    NASA Technical Reports Server (NTRS)

    Scott, Carl D.; Smalley, Richard E.

    2002-01-01

    The high-pressure carbon monoxide (HiPco) process for producing single-wall carbon nanotubes (SWNT) uses iron pentacarbonyl as the source of iron for catalyzing the Boudouard reaction. Attempts using nickel tetracarbonyl led to no production of SWNTs. This paper discusses simulations at a constant condition of 1300 K and 30 atm in which the chemical rate equations are solved for different reaction schemes. A lumped cluster model is developed to limit the number of species in the models, yet it includes fairly large clusters. Reaction rate coefficients in these schemes are based on bond energies of iron and nickel species and on estimates of chemical rates for formation of SWNTs. SWNT growth is measured by the co-formation of CO2. It is shown that the production of CO2 is significantly greater for FeCO due to its lower bond energy as compared with that ofNiCO. It is also shown that the dissociation and evaporation rates of atoms from small metal clusters have a significant effect on CO2 production. A high rate of evaporation leads to a smaller number of metal clusters available to catalyze the Boudouard reaction. This suggests that if CO reacts with metal clusters and removes atoms from them by forming MeCO, this has the effect of enhancing the evaporation rate and reducing SWNT production. The study also investigates some other reactions in the model that have a less dramatic influence.

  11. Structural, theoretical and corrosion inhibition studies on some transition metal complexes derived from heterocyclic system

    NASA Astrophysics Data System (ADS)

    Gupta, Shraddha Rani; Mourya, Punita; Singh, M. M.; Singh, Vinod P.

    2017-06-01

    A Schiff base, (E)-N‧-((1H-indol-3-yl)methylene)-2-aminobenzohydrazide (Iabh) and its Mn(II), Co(II), Ni(II), Cu(II) and Zn(II) complexes have been synthesized. These compounds have been characterized by different physico-chemical and spectroscopic tools (UV-Vis, IR, NMR and ESI-Mass). The molecular structure of Iabh is determined by single crystal X-ray diffraction technique. The ligand Iabh displays E-configuration about the >Cdbnd N- bond. The structure of ligand is stabilized by intra-molecular H-bonding. In all the metal complexes the ligand coordinates through azomethine-N and carbonyl-O resulting a distorted octahedral geometry for Mn(II), Co(II) and Cu(II) complexes in which chloride ions occupy axial positions. Ni(II) and Zn(II) complexes, however, form 4-coordinate distorted square planer and tetrahedral geometry around metal ion, respectively. The structures of the complexes have been satisfactorily modeled by calculations based on density functional theory (DFT) and time dependent-DFT (TD-DFT). The corrosion inhibition study of the compounds have been performed against mild steel in 0.5 M H2SO4 solution at 298 K by using weight loss, potentiodynamic polarization and electrochemical impedance spectroscopy (EIS). They show appreciable corrosion inhibition property.

  12. Tetrel, chalcogen, and CH⋅⋅O hydrogen bonds in complexes pairing carbonyl-containing molecules with 1, 2, and 3 molecules of CO{sub 2}

    SciTech Connect

    Azofra, Luis M.; Scheiner, Steve

    2015-01-21

    The complexes formed by H{sub 2}CO, CH{sub 3}CHO, and (CH{sub 3}){sub 2}CO with 1, 2, and 3 molecules of CO{sub 2} are studied by ab initio calculations. Three different types of heterodimers are observed, most containing a tetrel bond to the C atom of CO{sub 2}, and some supplemented by a CH⋅⋅O H-bond. One type of heterodimer is stabilized by an anti-parallel arrangement of the C=O bonds of the two molecules. The binding energies are enhanced by methyl substitution on the carbonyl, and vary between 2.4 and 3.5 kcal/mol. Natural bond orbital analysis identifies a prime source of interaction as charge transfer into the π*(CO) antibonding orbital. Heterotrimers and tetramers carry over many of the geometrical and bonding features of the binary complexes, but also introduce O⋅⋅O chalcogen bonds. These larger complexes exhibit only small amounts of cooperativity.

  13. Determination of melamine in different milk batches using a novel chemosensor based on the luminescence quenching of Ru(II) carbonyl complex.

    PubMed

    Attia, M S; Bakir, E; Abdel-aziz, Ayman A; Abdel-mottaleb, M S A

    2011-03-15

    A novel, simple, sensitive and precise spectrofluorimetric method was developed for measuring the melamine concentration in different milk batch samples. The method was based upon measuring the quenching of the luminescence intensity of the produced yellow colored ruthenium((II)) carbonyl complex of the general formula [Ru(CO)(2)(L)] (where L=anion of tetradentate Schiff base). The Ru((II)) complex exhibited characteristic luminescence band in the visible region. The remarkable quenching of the luminescence intensity of [Ru(CO)(2)(L)] complex by various concentrations of melamine was successfully used as a chemosensor for the assessment of melamine in different milk samples at λ(ex)=400 nm and pH 7.4 in DMSO with a linear dynamic range 1.0 × 10(-6) to 3.0 × 10(-9) mol L(-1) and lower detection limit (LOD) and quantification detection limit (QOD) of 3.3 × 10(-10) and 1.0 × 10(-9) mol L(-1), respectively.

  14. Characterization of the metal-support interface in supported metal and supported metal complex catalysts. [Final report

    SciTech Connect

    Gates, B.C.

    1992-12-31

    Re and Ir carbonyls, and other compounds, were chosen as precursors. MgO, La{sub 2}O{sub 3}, zeolite NaX and KL, among others, were chosen as supports. EXAFS was used to study the metal-support interactions. Structures formed on almost fully dehydroxylated MgO by HRe(CO){sub 5}, and on MgO by Ir{sub 4}(CO){sub 12}, were studied. A metal-oxygen distance of 2.15 {angstrom} holds in for the metal-support interface in oxide-supported metal clusters following reduction in H{sub 2} above 450 C; for reduction below 350 C, the distance is 2.5--2.7 {angstrom}.

  15. Unusual saccharin-N,O (carbonyl) coordination in mixed-ligand copper(II) complexes: Synthesis, X-ray crystallography and biological activity

    NASA Astrophysics Data System (ADS)

    Mokhtaruddin, Nur Shuhada Mohd; Yusof, Enis Nadia Md; Ravoof, Thahira B. S. A.; Tiekink, Edward R. T.; Veerakumarasivam, Abhi; Tahir, Mohamed Ibrahim Mohamed

    2017-07-01

    Three tridentate Schiff bases containing N and S donor atoms were synthesized via the condensation reaction between S-2-methylbenzyldithiocarbazate with 2-acetyl-4-methylpyridine (S2APH); 4-methyl-3-thiosemicarbazide with 2-acetylpyridine (MT2APH) and 4-ethyl-3-thiosemicarbazide with 2-acetylpyridine (ET2APH). Three new, binuclear and mixed-ligand copper(II) complexes with the general formula, [Cu(sac)(L)]2 (sac = saccharinate anion; L = anion of the Schiff base) were then synthesized, and subsequently characterized by IR and UV/Vis spectroscopy as well as by molar conductivity and magnetic susceptibility measurements. The Schiff bases were also spectroscopically characterized using NMR and MS to further confirm their structures. The spectroscopic data indicated that the Schiff bases behaved as a tridentate NNS donor ligands coordinating via the pyridyl-nitrogen, azomethine-nitrogen and thiolate-sulphur atoms. Magnetic data indicated a square pyramidal environment for the complexes and the conductivity values showed that the complexes were essentially non-electrolytes in DMSO. The X-ray crystallographic analysis of one complex, [Cu(sac)(S2AP)]2 showed that the Cu(II) atom was coordinated to the thiolate-S, azomethine-N and pyridyl-N donors of the S2AP Schiff base and to the saccharinate-N from one anion, as well as to the carbonyl-O atom from a symmetry related saccharinate anion yielding a centrosymmetric binuclear complex with a penta-coordinate, square pyramidal geometry. All the copper(II) saccharinate complexes were found to display strong cytotoxic activity against the MCF-7 and MDA-MB-231 human breast cancer cell lines.

  16. Chiral bis(oxazoline) copper(II) complexes: versatile catalysts for enantioselective cycloaddition, Aldol, Michael, and carbonyl ene reactions.

    PubMed

    Johnson, J S; Evans, D A

    2000-06-01

    A bis(oxazoline) (box) copper(II) complex and its hydrated counterpart (1 and 2) function as enantioselective Lewis acid catalysts for carbocyclic and hetero Diels-Alder, aldol, Michael, ene, and amination reactions with substrates capable of chelation through six- and five-membered rings. X-ray crystallography of the chiral complexes reveals a propensity for the formation of distorted square planar or square pyramidal geometries. The sense of asymmetric induction is identical for all the processes catalyzed by [Cu((S,S)-t-Bu-box)](X)(2) complexes 1 and 2 (X = OTf and SbF) resulting from the intervention of a distorted square planar catalyst-substrate binary complex. These catalyzed processes exhibit excellent temperature-selectivity profiles. Reactions catalyzed by [Cu(S,S-Ph-pybox)](SbF(6))(2) and their derived chelation complexes are also discussed.

  17. Preparation, spectroscopy, EXAFS, electrochemistry and pharmacology of new ruthenium(II) carbonyl complexes containing ferrocenylthiosemicarbazone and triphenylphosphine/arsine

    NASA Astrophysics Data System (ADS)

    Prabhakaran, R.; Anantharaman, S.; Thilagavathi, M.; Kaveri, M. V.; Kalaivani, P.; Karvembu, R.; Dharmaraj, N.; Bertagnolli, H.; Dallemer, F.; Natarajan, K.

    2011-02-01

    A new series of new hetero-bimetallic complexes containing iron and ruthenium of the general formula [RuCl(CO)(B)(EPh 3)(L)] (where E = P or As; B = PPh 3, AsPh 3, py or pip; L = ferrocene derived monobasic bidentate thiosemicarbazone ligand) have been synthesized by the reaction between ferrocene-derived thiosemicarbazones and ruthenium(II) complexes of the type [RuHCl(CO)(B)(EPh 3) 2] (where E = P or As; B = PPh 3, AsPh 3, py or pip). The new complexes have been characterized by elemental analyses, IR, electronic, NMR ( 1H, 13C and 31P), EXAFS (extended X-ray absorption fine structure spectroscopy) and cyclic voltammetric techniques. Antibacterial activity of the new complexes has been screened against Escherichia coli, Vibrio cholerae, and Pseudomonas aeruginosa species.

  18. Energetic characteristics of transition metal complexes.

    PubMed

    Wojewódka, Andrzej; Bełzowski, Janusz; Wilk, Zenon; Staś, Justyna

    2009-11-15

    Ten transition metal nitrate and perchlorate complexes of hydrazine and ethylenediamine were synthesized, namely [Cu(EN)(2)](ClO(4))(2), [Co(EN)(3)](ClO(4))(3), [Ni(EN)(3)](ClO(4))(2), [Hg(EN)(2)](ClO(4))(2), [Cr(N(2)H(4))(3)](ClO(4))(3), [Cd(N(2)H(4))(3)](ClO(4))(2), [Ni(N(2)H(4))(3)](NO(3))(2), [Co(N(2)H(4))(3)](NO(3))(3), [Zn(N(2)H(4))(3)](NO(3))(2), and [Cd(N(2)H(4))(3)](NO(3))(2) based on the lines of the literature reported methods. All of them were tested with applying underwater detonation test and further compared to the typical blasting explosives: RDX, HMX, TNT and PETN. From the above presented complexes [Ni(N(2)H(4))(3)](NO(3))(2) (called NHN) and [Co(N(2)H(4))(3)](NO(3))(3) (called CoHN) are known as primary explosives and can be used as the standard explosives. Explosion parameters, such as shock wave overpressure, shock wave energy equivalent and bubble energy equivalent, were determined. Evaluated energetic characteristics of the tested compounds are comparable to those of the classic high explosives and are even enhanced in some cases.

  19. Evaluation of DNA cleavage, antimicrobial and anti-tubercular activities of potentially active transition metal complexes derived from 2,6-di(benzofuran-2-carbohydrazono)-4-methylphenol

    NASA Astrophysics Data System (ADS)

    Kokare, Dhoolesh Gangaram; Kamat, Vinayak; Naik, Krishna; Nevrekar, Anupama; Kotian, Avinash; Revankar, Vidyanand K.

    2017-01-01

    A 2,6-diformyl-4-methyl phenol based multidentate novel symmetric ligand and it is late first-row transition metal complexes have been prepared. The ligand and metal complexes were characterized by different spectroscopic techniques. The ligand shows a symmetric polydentate coordination mode through the phenoxide bimetallic bridge, two azomethine nitrogen atoms and two carbonyl oxygen atoms. All the complexes appear to be binuclear with octahedral geometry and nonelectrolytic nature. Complexes have shown significant growth inhibitory activity against tested bacterial and fungal strains as compared to that of ligand. The cobalt complex exhibited better antifungal potency than the standard used. Copper complex exhibits good antifungal activity whereas cobalt and zinc complexes are found to be good antibacterial agents. Ligand and complexes have shown excellent anti-tubercular activity and Calf Thymus-DNA cleavage property.

  20. Synthesis and structural characterization of ruthenium carbonyl cluster complexes containing platinum with a bulky N-heterocyclic carbene ligand.

    PubMed

    Saha, Sumit; Captain, Burjor

    2014-01-21

    The reaction of Ru3(CO)12 with Pt(IMes)2 in benzene solvent at room temperature afforded the monoplatinum-triruthenium cluster complex Ru3Pt(IMes)2(CO)11, 1, in 21% yield and the trigonal bipyramidal cluster complex Ru3Pt2(IMes)2(CO)12, 2, in 26% yield. The reaction of Ru(CO)5 with Pt(IMes)2 in benzene solvent at 0 °C yielded two trinuclear cluster complexes, the monoplatinum-diruthenium Ru2Pt(IMes)(CO)9, 3, and the monoruthenium-diplatinum cluster complex RuPt2(IMes)2(CO)6, 4. The reaction of 2 with hydrogen at 80 °C afforded the tetrahydrido-tetraruthenium complex Ru4(IMes)(CO)11(μ-H)4, 5, and the dihydrido-diruthenium-diplatinum complex Ru2Pt2(IMes)2(CO)8(μ-H)2, 6. All six compounds were structurally characterized by single-crystal X-ray diffraction analyses.

  1. Molecular Orbital, Generalized Valence Bond, and Complete Active Space Calculations on Transition Metal Compounds with Agostic Hydrogen and Bridging Carbonyls: New Basis Sets, Geometry of Trichloromethyltitanium, and Bonding of bis

    NASA Astrophysics Data System (ADS)

    Williamson, Rodney Lowell

    Total geometry optimizations are reported for Cr(CO)_6, HMn(CO)_5 , Fe(CO)_5, Ni(CO) _4, Cr(C_6H _6)_2, Fe(C_5H _5)_2, Ni(C_4 H_4)_2, Cr(NO) _4, (C_5H _5)Mn(CO)_3, and (C _6H_6)Cr(CO) _3. A variety of basis sets were examined, and, based on the results, a relatively compact and accurate basis set is proposed. Addition of electron correlation at the perfect pairing GVB level reduced the average difference in the metal-cyclopentadienyl bond length of 0.08 A. Optimization of the geometry of TiCl_4 and TiCl_3CH_3 at the self-consistent-field (SCF) level results in Ti-Cl bond lengths longer than the experimental values, even when d- and f-type polarization functions are added to the basis set. The bond lengths remain too long even as the Hartree-Fock limit is approached because the SCF level of theory over-estimates the noble-gas-like Cl cdotsCl repulsions, which hinder close Ti -Cl approach. The Ti-C-H angle of TiCl_3 CH_3 is calculated to be close to tetrahedral geometry with little flattening of the hydrogen atoms, which apparently was observed in the electron diffraction. These same calculations do predict the anomalously low methyl-rocking frequency for the titanium complex in agreement with the experimental IR. The large positive geminal hydrogen coupling constant observed in the NMR experiment is due primarily to the sigma -donor and pi-acceptor character of the TiCl_3 moiety and not to any flattening of the methyl group. The structure and bonding of (Cr(Cp)(CO) _2) _2 was examined by optimizing the geometry of the dimer, fragment moiety, and analogous stable monomers. The optimized structure of Cr(Cp)(CO)_2N has a "piano stool" geometry with a fragment moiety geometry nearly identical to the geometry of the fragment moiety in the dimer. Examination of x-ray and theoretical geometries of monomers with the fragment moiety bonded to single ligand show that the geometry of the fragment moiety is insensitive to the ligands bonded to it. Van der Waals calculations

  2. New ruthenium(II) carbonyl complexes bearing disulfide Schiff base ligands and their applications as catalyst for some organic transformations

    NASA Astrophysics Data System (ADS)

    Prakash, Govindan; Viswanathamurthi, Periasamy

    2014-08-01

    Schiff base disulfide ligands (H2L1-6) were synthesized from the condensation of cystamine with salicylaldehyde(H2L1), 5-chlorosalicylaldehyde(H2L2), o-vanillin(H2L3), 2-hydroxyacetophenone(H2L4), 3-methyl-2-hydroxyacetophenone(H2L5), and 2-hydroxy-1-naphthaldehyde(H2L6). H2L1-6 reacts with the ruthenium precursor complex [RuHCl(CO)(PPh3)3] in benzene giving rise to six new ruthenium(II) complexes of general formula [Ru(CO)L1-6]. Characterization of the new complexes was carried out by using elemental and spectral (IR, UV-Vis, NMR (1H and 13C) and Mass) techniques. An octahedral geometry was assigned for all the complexes based on the spectral data obtained. The catalytic efficiency of the new complexes in aldehyde to amide conversion in the presence of NaHCO3, N-alkylation of aniline in the presence of t-BuOK, and transfer hydrogenation of ketones in the presence of iPrOH/KOH reactions were studied. Furthermore, the effect of solvents and catalyst/substrate ratio on the catalytic aldehyde to amide conversion were also discussed.

  3. New ruthenium(II) carbonyl complexes bearing disulfide Schiff base ligands and their applications as catalyst for some organic transformations.

    PubMed

    Prakash, Govindan; Viswanathamurthi, Periasamy

    2014-08-14

    Schiff base disulfide ligands (H2L(1-6)) were synthesized from the condensation of cystamine with salicylaldehyde(H2L(1)), 5-chlorosalicylaldehyde(H2L(2)), o-vanillin(H2L(3)), 2-hydroxyacetophenone(H2L(4)), 3-methyl-2-hydroxyacetophenone(H2L(5)), and 2-hydroxy-1-naphthaldehyde(H2L(6)). H2L(1-6) reacts with the ruthenium precursor complex [RuHCl(CO)(PPh3)3] in benzene giving rise to six new ruthenium(II) complexes of general formula [Ru(CO)L(1-6)]. Characterization of the new complexes was carried out by using elemental and spectral (IR, UV-Vis, NMR ((1)H and (13)C) and Mass) techniques. An octahedral geometry was assigned for all the complexes based on the spectral data obtained. The catalytic efficiency of the new complexes in aldehyde to amide conversion in the presence of NaHCO3, N-alkylation of aniline in the presence of t-BuOK, and transfer hydrogenation of ketones in the presence of iPrOH/KOH reactions were studied. Furthermore, the effect of solvents and catalyst/substrate ratio on the catalytic aldehyde to amide conversion were also discussed.

  4. Synthesis, spectroscopic, DFT calculations and biological activity studies of ruthenium carbonyl complexes with 2-picolinic acid and a secondary ligand

    NASA Astrophysics Data System (ADS)

    Shohayeb, Shahera M.; Mohamed, Rania G.; Moustafa, H.; El-Medani, Samir M.

    2016-09-01

    Thermal reaction of [Ru3(CO)12] with 2-picolinic acid (Hpic) in the absence and presence of a secondary ligand (pyridine, Py, bipyridine, Bipy, or thiourea, Tu) was investigated. Four complexes with molecular formulae: [Ru(CO)3(Hpic)], 1, [Ru2(CO)5(Hpic)(Py)], 2, [Ru2(CO)5(Hpic)(Tu)], 3 and [Ru2(CO)4(Hpic)(Bipy)], 4, were isolated. All complexes were characterized based on elemental analyses, IR, 1H NMR, magnetic studies, mass spectrometry and thermal analysis. The ligand and its complexes have been screened for antibacterial activities. Density Functional Theory (DFT) calculations at the B3LYP/6-311G (d,p)_ level of theory have been carried out to investigate the equilibrium geometry of the ligands. The optimized geometry parameters of the complexes were evaluated using B3LYP method and LANL2DZ basis set. The extent of natural charge population (core, valence and rydberg), exact electronic configuration, total Lewis and total non-Lewis are estimated and discussed in terms of natural bond orbitals (NBO) analysis.

  5. Early Transition Metal Alkyl and Tetrahydroborate Complexes.

    NASA Astrophysics Data System (ADS)

    Jensen, James Allen

    1988-06-01

    An investigation of early transition metal alkyl and tetrahydroborate complexes as catalytic models and ceramic precursors has been initiated. The compounds MX _2 (dmpe)_2, dmpe = 1,2-bis(dimethylphosphino)ethane, for M = Ti, V, Cr, and X = Br, I, BH_4, have been prepared. These complexes are paramagnetic and have been shown by X-ray crystallography to have trans-octahedral structures. The BH_4^{-} groups in Ti(BH_4)_2(dmpe) _2 bond to the metal in a bidentate manner. This structure is in marked contrast to the structure of the vanadium analogue, V(BH_4)_2 (dmpe)_2, which displays two unidentate BH_4^{-} groups. Alkylation of Ti(BH_4)_2 (dmpe)_2 with LiMe results in the complex TiMe_2(dmpe) _2 which is diamagnetic in both solution and solid state. Single crystal X-ray and neutron diffraction studies show that there may be strong Ti-C pi -bonding. A tetragonal compression along the C -Ti-C bond vector accounts for the observed diamegnetism. A series of complexes of the formula Ti(BH _4)_3(PR_3)_2 has been prepared where PR_3 = PMe_3, PEt_3, PMe_3Ph, and P(OMe)_3 . The X-ray crystal structure of Ti(BH _4)_3(PMe_3)_2 reveals a pseudo trigonal bipyramidal geometry in which two BH_4^{-} groups display an unusual "side-on" bonding mode. The "side-on" ligation mode has been attributed to a Jahn-Teller distortion of the orbitally degenerate d^1 ground state. In contrast, the non-Jahn-Teller susceptible vanadium analogue, V(BH_4)_3 (PMe_3)_2, possesses a nearly ideal D_{rm 3h} >=ometry with three bidentate tetrahydroborate groups. Addition of excess PMe_3 to V(BH_4)_3(PMe _3)_2<=ads to the vanadium(II) hydride -bridged dimer (V(H)(BH_4)(PMe _3)_2]_2, while addition of PMe_3 and water forms the vanadium(III) oxo dimer (V(BH_4)_2 (PMe_3)_2]_2 [mu-O) which has been structurally characterized. The compound Ti(CH_2CMe _3)_4 can be prepared by addition of Ti(OEt)_4 to LiCH_2 CMe_3. Sublimation of Ti(CH _2CMe_3)_4 over a substrate heated to 250^ circC results in the chemical vapor

  6. ProPhenol-Catalyzed Asymmetric Additions by Spontaneously Assembled Dinuclear Main Group Metal Complexes

    PubMed Central

    2016-01-01

    Conspectus The development of catalytic enantioselective transformations has been the focus of many research groups over the past half century and is of paramount importance to the pharmaceutical and agrochemical industries. Since the award of the Nobel Prize in 2001, the field of enantioselective transition metal catalysis has soared to new heights, with the development of more efficient catalysts and new catalytic transformations at increasing frequency. Furthermore, catalytic reactions that allow higher levels of redox- and step-economy are being developed. Thus, alternatives to asymmetric alkene dihydroxylation and the enantioselective reduction of α,β-unsaturated ketones can invoke more strategic C–C bond forming reactions, such as asymmetric aldol reactions of an aldehyde with α-hydroxyketone donors or enantioselective alkynylation of an aldehyde, respectively. To facilitate catalytic enantioselective addition reactions, including the aforementioned aldol and alkynylation reactions, our lab has developed the ProPhenol ligand. In this Account, we describe the development and application of the ProPhenol ligand for asymmetric additions of both carbon- and heteroatom-based nucleophiles to various electrophiles. The ProPhenol ligand spontaneously forms chiral dinuclear metal complexes when treated with an alkyl metal reagent, such as Et2Zn or Bu2Mg. The resulting complex contains both a Lewis acidic site to activate an electrophile and a Brønsted basic site to deprotonate a pronucleophile. Initially, our research focused on the use of Zn-ProPhenol complexes to facilitate the direct aldol reaction. Fine tuning of the reaction through ligand modification and the use of additives enabled the direct aldol reaction to proceed in high yields and stereoselectivities with a broad range of donor substrates, including acetophenones, methyl ynones, methyl vinyl ketone, acetone, α-hydroxy carbonyl compounds, and glycine Schiff bases. Additionally, an analogous

  7. Metal complexes and metalloproteases: targeting conformational diseases.

    PubMed

    Grasso, Giuseppe; Bonnet, Sylvestre

    2014-08-01

    In recent years many metalloproteases (MPs) have been shown to play important roles in the development of various pathological conditions. Although most of the literature is focused on matrix MPs (MMPs), many other MPs have been demonstrated to be involved in the degradation of peptides or proteins whose accumulation and dyshomeostasis are considered as being responsible for the development of conformational diseases, i.e., diseases where non-native protein conformations lead to protein aggregation. It seems clear that, at least in principle, it must be possible to control the levels of many aggregation-prone proteins not only by reducing their production, but also by enhancing their catabolism. Metal complexes that can perform this function were designed and tested according to at least two different strategies: (i) intervening on the endogenous MPs by directly or indirectly modulating their activity; (ii) acting as artificial MPs, replacing or synergistically functioning with endogenous MPs. These two different bioinorganic approaches are widely represented in the current literature and the aim of this review is to rationally organize and discuss both of them so as to give a critical insight into these approaches and highlighting their limitations and future perspectives.

  8. Exploring the Mechanism of Ultrafast Intersystem Crossing in Rhenium(I) Carbonyl Bipyridine Halide Complexes: Key Vibrational Modes and Spin-Vibronic Quantum Dynamics.

    PubMed

    Harabuchi, Yu; Eng, Julien; Gindensperger, Etienne; Taketsugu, Tetsuya; Maeda, Satoshi; Daniel, Chantal

    2016-05-10

    The mechanism of ultrafast intersystem crossing in rhenium(I) carbonyl bipyridine halide complexes Re(X)(CO)3(bpy) (X = Cl, Br, I) is studied by exploring the structural deformations when going from Franck-Condon (FC) to critical geometries in the low-lying singlet and triplet excited states and by selecting the key vibrational modes. The luminescent decay observed in [Re(Br)(CO)3(bpy)] is investigated by means of wavepacket propagations based on the multiconfiguration time-dependent Hartree (MCTDH) method. The dominant coordinates underlying the nonradiative decay process are extracted from minima, minimum energy seam of crossing (MESX) and minimum energy conical intersection (MECI) geometries obtained by the seam model function (SMF)/single-component artificial force induced reaction (SC-AFIR) approach. By choosing the normal modes used in MCTDH from the MECI and MESX geometries, not only the degenerate energy points but also the low-energy-gap regions are included. For this purpose a careful vibrational analysis is performed at each critical geometry and analyzed under the light of the pertinent nonadiabatic coupling terms obtained from the linear vibronic coupling (LVC) model augmented by spin-orbit coupling (SOC) in the electronic diabatic representation.

  9. Recent Researches in Metal Supramolecular Complexes as Anticancer Agents.

    PubMed

    Zhou, Cheng-He; Zhang, Yi-Yi; Yan, Cong-Yan; Wan, Kun; Gan, Lin-Ling; Shi, Yuan

    2010-04-12

    The research and development of metal supramolecular complexes as anticancer supramolecular drugs, which are aggregates mainly formed by one or more inorganic metal compounds with one or more either inorganic or organic molecules in general via coordination bonds, has been a quite rapidly developing, increasingly active and newly rising highlight interdisciplinary field. Numerous efforts have been directed toward metal supramolecular complexes as potential anticancer agents and the unprecedented progress has been made. This has opened up a wholly new and infinite space to create novel metal-based bioactive supermolecules. More importantly, metal-based complex supermolecules as potential anticancer agents with wide potential applications have become highlight topics in recent years, and are becoming increasingly useful and important in preventing and treating cancer diseases. In view of the rapid progress in metal complex anticancer supermolecules with rich variation of structural types, this work systematically reviewed the recent research and development of the whole range of metal-based supramolecular complexes as anticancer agents mainly in 2009. The perspectives of the foreseeable future and potential application of metal supramolecular complexes in cancer therapy were also presented. It is hoped that this review will serve as a stimulant for new thoughts in the quest for rational designs of more active and less toxic metal supramolecular complex anticancer drugs.

  10. Recent researches in metal supramolecular complexes as anticancer agents.

    PubMed

    Zhou, Cheng-He; Zhang, Yi-Yi; Yan, Cong-Yan; Wan, Kun; Gan, Lin-Ling; Shi, Yuan

    2010-06-01

    The research and development of metal supramolecular complexes as anticancer supramolecular drugs, which are aggregates mainly formed by one or more inorganic metal compounds with one or more either inorganic or organic molecules in general via coordination bonds, has been a quite rapidly developing, increasingly active and newly rising highlight interdisciplinary field. Numerous efforts have been directed toward metal supramolecular complexes as potential anticancer agents and the unprecedented progress has been made. This has opened up a wholly new and infinite space to create novel metal-based bioactive supermolecules. More importantly, metal-based complex supermolecules as potential anticancer agents with wide potential applications have become highlight topics in recent years, and are becoming increasingly useful and important in preventing and treating cancer diseases. In view of the rapid progress in metal complex anticancer supermolecules with rich variation of structural types, this work systematically reviewed the recent research and development of the whole range of metal-based supramolecular complexes as anticancer agents mainly in 2009. The perspectives of the foreseeable future and potential application of metal supramolecular complexes in cancer therapy were also presented. It is hoped that this review will serve as a stimulant for new thoughts in the quest for rational designs of more active and less toxic metal supramolecular complex anticancer drugs.

  11. Hydrosilation of Carbonyl-Containing Substrates Catalyzed by an Electrophilic η1-Silane Iridium(III) Complex

    PubMed Central

    Park, Sehoon; Brookhart, Maurice

    2010-01-01

    Hydrosilation of a variety of ketones and aldehydes using the cationic iridium catalyst, (POCOP)Ir(H)(acetone)+, 1, (POCOP = 2,6-bis(di-tert-butyl phosphinito)phenyl) is reported. With triethyl silane, all but exceptionally bulky ketones undergo quantitative reactions employing 0.5 mol% catalyst in 20-30 min at 25 °C. Hydrosilation of esters and amides results in over-reduction and cleavage of C-O and C-N bonds, respectively. The diastereoselectivity of hydrosilation of 4-tert-butyl cyclohexanone has been examined using numerous silanes and is highly temperature dependent. Using EtMe2SiH, analysis of the ratio of cis:trans hydrosilation products as a function of temperature yields values for ΔΔH‡ (ΔH‡ (trans) - ΔH‡ (cis)) and ΔΔS‡ (ΔS‡ (trans) - ΔS‡(cis)) of -2.5 kcal/mol and -6.9 e.u., respectively. Mechanistic studies show that the ketone complex, (POCOP)Ir(H)(ketone)+, is the catalyst resting state and is in equilibrium with low concentration of the silane complex, (POCOP)Ir(H)(HSiR3)+. The silane complex transfers R3Si+ to ketone forming the oxocarbenium ion, R3SiOCR’2+, which is reduced by the resulting neutral dihydride 3, (POCOP)Ir(H)2, to yield product R3SiOCHR’2 and (POCOP)IrH+ which closes the catalytic cycle. PMID:21572562

  12. Photochemistry of Cobalt Carbonyl Complexes having a Cobalt-Silicon Bond and its Importance in Activation of Catalysis.

    DTIC Science & Technology

    1980-08-22

    5 equation (4). These complexes are Co2 (CO)8 + 2HSiR 3 - 2R3SiCo(CO)4 + H2 (4) R = Et, Ph thermally inert at 250C in deoxygenated hydrocarbon...of Ph3SiCo(CO)4 in the presence of HSiEt 3only (a) and HSiEt 3 and P(OPh) 3 (b). Irradiation of the 25C deoxygenated solutions is at 355 nm (+ 20 nm...North Quincy Street P.O. Fox 1211 Arlington, Virginia 22217 2 Research Triangle Park, N.C. 27709 1 ONR Branch Office Naval Ocean Systems Center Attn

  13. Eigen kinetics in surface complexation of aqueous metal ions.

    PubMed

    van Leeuwen, Herman P

    2008-10-21

    The mechanism of chemisorption of aqueous metal ions at surfaces has long been a topical issue in such fields as soil chemistry and bioenvironmental science. Here it is quantitatively demonstrated for the first time that release of water from the inner hydration shell is the rate-limiting step in inner-sphere surface complexation. The reactive intermediate is an outer-sphere complex between metal ion and surface site, with an electrostatically controlled stability defined by Boltzmann statistics. Using tabulated dehydration rate constants for metal ions, the resulting scheme allows for prediction of rates of sorption of aqueous metal ions at any type of complexing surface.

  14. Alkoxy-Siloxide Metal Complexes: Precursors to Metal Silica, Metal Oxide Silica, and Metal Silicate Materials.

    NASA Astrophysics Data System (ADS)

    Terry, Karl William

    The alkoxy-siloxide complexes M (OSi(O ^{rm t}Bu)_3 ]_4 (M = Ti(1), Zr(2), Hf(3)), were prepared by reaction with their respective metal diethylamides. These compounds readily undergo low-temperature decomposition to their respective metal oxide silica materials rm(MO_2{cdot}4SiO_2). The volatile products of the thermolysis of 2 (ca. 200 ^circC) were isobutylene (11.7 equiv) and water (5.4 equiv). The rm ZrO _2{cdot}4SiO_2 material from the decomposition of 2 at 400^circ C was amorphous until ca. 1100^ circC where crystallization of t-ZrO _2 occurred. After thermolysis to 1500 ^circC, t-ZrO_2 and cristobalite were the major products with minor amounts of m-ZrO_2. The rm HfO_2{cdot}4SiO_2 material from the decomposition of 3 at 400^ circC was amorphous until ca. 1000 ^circC where crystallization of c/t -HfO_2 was observed. Thermolysis to 1460^circC yielded c/t -HfO_2, m-HfO_2, and minor amounts of cristobalite. The crystallization of anatase in the rm TiO_2{cdot }4SiO_2 material from decomposed 1 at 400^circC was apparent after thermolysis to 1000^circC. Thermolysis to 1400^circC gave a mixture of anatase, rutile, and cristobalite. Compound 2 was decomposed in xylenes and yielded a transparent gel which was isolated as a white powder upon drying in vacuuo. The compounds [ Me _2AlOSi(O^{t}Bu)_3] _2 (4) and [( ^{t}BuO)MeAlOSi(O^{t}Bu) _3]_2 (5) were structurally characterized and contain bent and planar rm Al_2O_2 four membered rings, respectively. Both 4 and 5 yield isobutylene upon thermolysis (ca. 200 ^circC) and the crystallization of mullite occurs at 1034^circC and 1017^circC, respectively (by DTA). The solution thermolysis of 4 in refluxing toluene yields an opaque white gel. The crystallization of mullite occurs at 1029^circC (by DTA). The compounds [ CuOSi(O ^{t}Bu)_3]_{n } (6) and [ CuOSi(O ^{t}Bu)_2Ph]_4 (7) were prepared by reaction with [ CuO^{t}Bu]_4. The thermolysis of 6 at 1000^circ C under argon gave Cu^circ and amorphous silica and thermolysis under

  15. Pattern-based sensing with simple metal-dye complexes.

    PubMed

    Severin, Kay

    2010-12-01

    Different strategies for the creation of optical sensors with metal-dye complexes are discussed. The focus is on sensors, which are used in conjunction with pattern recognition protocols. It is shown that remarkably powerful sensors can be obtained by combining commercially available dyes with simple transition metal complexes. Copyright © 2010 Elsevier Ltd. All rights reserved.

  16. VCD studies on chiral characters of metal complex oligomers.

    PubMed

    Sato, Hisako; Yamagishi, Akihiko

    2013-01-07

    The present article reviews the results on the application of vibrational circular dichroism (VCD) spectroscopy to the study of stereochemical properties of chiral metal complexes in solution. The chiral characters reflecting on the vibrational properties of metal complexes are revealed by measurements of a series of β-diketonato complexes with the help of theoretical calculation. Attention is paid to the effects of electronic properties of a central metal ion on vibrational energy levels or low-lying electronic states. The investigation is further extended to the oligomers of β-diketonato complex units. The induction of chiral structures is confirmed by the VCD spectra when chiral inert moieties are connected with labile metal ions. These results have demonstrated how VCD spectroscopy is efficient in revealing the static and dynamic properties of mononuclear and multinuclear chiral metal complexes, which are difficult to clarify by means of other spectroscopes.

  17. VCD Studies on Chiral Characters of Metal Complex Oligomers

    PubMed Central

    Sato, Hisako; Yamagishi, Akihiko

    2013-01-01

    The present article reviews the results on the application of vibrational circular dichroism (VCD) spectroscopy to the study of stereochemical properties of chiral metal complexes in solution. The chiral characters reflecting on the vibrational properties of metal complexes are revealed by measurements of a series of β-diketonato complexes with the help of theoretical calculation. Attention is paid to the effects of electronic properties of a central metal ion on vibrational energy levels or low-lying electronic states. The investigation is further extended to the oligomers of β-diketonato complex units. The induction of chiral structures is confirmed by the VCD spectra when chiral inert moieties are connected with labile metal ions. These results have demonstrated how VCD spectroscopy is efficient in revealing the static and dynamic properties of mononuclear and multinuclear chiral metal complexes, which are difficult to clarify by means of other spectroscopes. PMID:23296273

  18. Unusual structure, fluxionality, and reaction mechanism of carbonyl hydrosilylation by silyl hydride complex [(ArN=)Mo(H)(SiH2Ph)(PMe3)3].

    PubMed

    Khalimon, Andrey Y; Ignatov, Stanislav K; Okhapkin, Andrey I; Simionescu, Razvan; Kuzmina, Lyudmila G; Howard, Judith A K; Nikonov, Georgii I

    2013-06-24

    The reactions of bis(borohydride) complexes [(RN=)Mo(BH4)2(PMe3)2] (4: R = 2,6-Me2C6H3; 5: R = 2,6-iPr2C6H3) with hydrosilanes afford new silyl hydride derivatives [(RN=)Mo(H)(SiR'3)(PMe3)3] (3: R = Ar, R'3 = H2Ph; 8: R = Ar', R'3 = H2Ph; 9: R = Ar, R'3 = (OEt)3; 10: R = Ar, R'3 = HMePh). These compounds can also be conveniently prepared by reacting [(RN=)Mo(H)(Cl)(PMe3)3] with one equivalent of LiBH4 in the presence of a silane. Complex 3 undergoes intramolecular and intermolecular phosphine exchange, as well as exchange between the silyl ligand and the free silane. Kinetic and DFT studies show that the intermolecular phosphine exchange occurs through the predissociation of a PMe3 group, which, surprisingly, is facilitated by the silane. The intramolecular exchange proceeds through a new non-Bailar-twist pathway. The silyl/silane exchange proceeds through an unusual Mo(VI) intermediate, [(ArN=)Mo(H)2(SiH2Ph)2(PMe3)2] (19). Complex 3 was found to be the catalyst of a variety of hydrosilylation reactions of carbonyl compounds (aldehydes and ketones) and nitriles, as well as of silane alcoholysis. Stoichiometric mechanistic studies of the hydrosilylation of acetone, supported by DFT calculations, suggest the operation of an unexpected mechanism, in that the silyl ligand of compound 3 plays an unusual role as a spectator ligand. The addition of acetone to compound 3 leads to the formation of [trans-(ArN)Mo(OiPr)(SiH2Ph)(PMe3)2] (18). This latter species does not undergo the elimination of a Si-O group (which corresponds to the conventional Ojima's mechanism of hydrosilylation). Rather, complex 18 undergoes unusual reversible β-CH activation of the isopropoxy ligand. In the hydrosilylation of benzaldehyde, the reaction proceeds through the formation of a new intermediate bis(benzaldehyde) adduct, [(ArN=)Mo(η(2)-PhC(O)H)2(PMe3)], which reacts further with hydrosilane through a η(1)-silane complex, as studied by DFT calculations.

  19. Synthesis and characterization of some transition metals polymer complexes

    NASA Astrophysics Data System (ADS)

    Masoud, Mamdouh S.; Abdou, Azza E. H.; Ahmed, Wael M.

    2015-09-01

    Co2+, Ni2+, Cu2+, Cr3+, Mn2+ and Fe3+ complexes of Polyacrylamide are prepared and characterized by elemental analyses, IR, UV-Vis spectra, magnetic measurements, and thermal analyses. The data suggests octahedral geometry for all complexes. The thermal behavior of the complexes has been studied applying TG, DTA, and DSC techniques, and the thermodynamic parameters and mechanisms of the decompositions were evaluated. The ΔS# values of the decomposition steps of the metal complexes indicated that the activated fragments have more ordered structure than the undecomposed complexes. The thermal processes proceeded in complicated mechanisms where the bond between the central metal ion and the ligands dissociates after losing 6(C2H5 N) and 6(CO), the metal complexes are ended with metal as a final product. Viscosity and Shale instability using liner swell meter were carried out. Comparisons of the experimental and theoretical IR spectra were also carried out besides some other theoretical calculations.

  20. Microwave irradiation for the facile synthesis of transition-metal nanoparticles (NPs) in ionic liquids (ILs) from metal-carbonyl precursors and Ru-, Rh-, and Ir-NP/IL dispersions as biphasic liquid-liquid hydrogenation nanocatalysts for cyclohexene.

    PubMed

    Vollmer, Christian; Redel, Engelbert; Abu-Shandi, Khalid; Thomann, Ralf; Manyar, Haresh; Hardacre, Christopher; Janiak, Christoph

    2010-03-22

    Stable chromium, molybdenum, tungsten, manganese, rhenium, ruthenium, osmium, cobalt, rhodium, and iridium metal nanoparticles (M-NPs) have been reproducibly obtained by facile, rapid (3 min), and energy-saving 10 W microwave irradiation (MWI) under an argon atmosphere from their metal-carbonyl precursors [M(x)(CO)(y)] in the ionic liquid (IL) 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIm][BF(4)]). This MWI synthesis is compared to UV-photolytic (1000 W, 15 min) or conventional thermal decomposition (180-250 degrees C, 6-12 h) of [M(x)(CO)(y)] in ILs. The MWI-obtained nanoparticles have a very small (<5 nm) and uniform size and are prepared without any additional stabilizers or capping molecules as long-term stable M-NP/IL dispersions (characterization by transmission electron microscopy (TEM), transmission electron diffraction (TED), and dynamic light scattering (DLS)). The ruthenium, rhodium, or iridium nanoparticle/IL dispersions are highly active and easily recyclable catalysts for the biphasic liquid-liquid hydrogenation of cyclohexene to cyclohexane with activities of up to 522 (mol product) (mol Ru)(-1) h(-1) and 884 (mol product) (mol Rh)(-1) h(-1) and give almost quantitative conversion within 2 h at 10 bar H(2) and 90 degrees C. Catalyst poisoning experiments with CS(2) (0.05 equiv per Ru) suggest a heterogeneous surface catalysis of Ru-NPs.

  1. The chemistry of carbonyl sulfide: Final report, July 1, 1985-February 28, 1986

    SciTech Connect

    Dunkerton, L.V.; Tyrrell, J.; Sasa, M.; Combariza, J.

    1986-05-01

    Molecular orbital calculations using effective core potential (ECP) have been carried out on a variety of complexes of carbonyl sulfide (OCS) with transition metals (Pd and Pt). An initial scan of the potential energy surface (the geometry for the carbonyl sulfide molecule was held constant at its experimental values) was carried out in order to determine the most probable sites for the attack of the transition matal on the carbonyl sulfide molecule. Two sites were shown to be energetically favorable: the approach of the transition metal towards the oxygen atom along the internuclear axis and the approach of the transition metal above or below the C-S bond region. After optimization of these two structures, the second minima was shown to be energetically more stable than the linear arrangement. In this optimum structure, the carbonyl sulfide molecule is bent. The higher affinity of palladium and platinum towards sulfur is shown in the tendency of these transition metal to form eta/sup 2 -/(OCS) type of bonds, in the order Pt > Pd. Dialkylaluminumchloride (R/sub 2/AlCl)-catalyzed ene reactions of carbonyl sulfide as an enophile with alkenes were performed. R/sub 2/AlCl selectively complexed to the thionyl sulfur of OCS, then reacted with different alkenes and formed corresponding alkenyl thioicacids as ene adducts. Those alkenes were limonene (1), ..beta..-pinene (2), and methylenecyclohexane (3). The reaction with 1 gave E and Z 3-(4 -(1'-hydroxy-1' -methyl-cyclohexyl))but-2-ene thiocacid (4) as a major product, which was formed from hydration of the thioicacid, a rearranged conjugated form of the original ene adduct. The reaction with 2 and 3 gave corresponding ..beta..,..gamma..-unsaturated original thioicacids, 2-(2'-(6',6'-dimethylbicyclo(3.1.1)hept-2'-ene))ethane thioicacid (5) and 2-(1' -cyclohexenyl)ethane thioicacid (6), respectively, as major products. 23 refs, 6 tabs.

  2. Structural diversity in binuclear complexes of alkaline earth metal ions with 4,6-diacetylresorcinol

    NASA Astrophysics Data System (ADS)

    Shebl, Magdy; Khalil, Saied M. E.; Taha, A.; Mahdi, M. A. N.

    2012-11-01

    A new series of binuclear and mixed-ligand complexes with the general formula: [M 2(LO)yClz]; where M = Mg(II), Ca(II), Sr(II) and Ba(II); H2L = 4,6-diacetylresorcinol, the secondary ligand L' = acetylacetone (acac), 8-hydroxyquinoline (8-HQ) or 2,2'-bipyridyl (Bipy), n = 0-2, m = 1, 2, x = 0, 1, 2, 4, y = 0, 2, 4, 5 and z = 0-2; have been synthesized. They have been characterized by the analytical and spectral methods (IR, 1H NMR and mass) as well as TGA and molar conductivity measurements. The spectroscopic and conductance data suggested that the H2L ligand behaves as a neutral, monobasic or dibasic tetradentate ligand, depending on the basicity of the secondary ligand, through the two phenolic and two carbonyl groups. Binuclear octahedral geometry has been assigned to all of the prepared complexes in various molar ratios 2:2; 2:2:2; 1:2:1 and 1:2:4 (L:M:L'). Molecular orbital calculations were performed for the ligands and their complexes using Hyperchem 7.52 program on the bases of PM3 level and the results were correlated with the experimental data. The ligand and some of its alkaline metal(II) complexes showed antibacterial activity towards some of Gram-positive and Gram-negative bacteria, yeast (Candida albicans) and fungus (Aspergillus fumigatus).

  3. Spectroscopic Characterization of Metal-Based Complexes and Metal-Based Complex Oxidation Processes.

    NASA Astrophysics Data System (ADS)

    McQuaid, Michael James

    The entrainment in carbon monoxide of metal (M) vaporized from an oven based source was used to create M(CO)_{rm x} complexes. The optical signatures associated with their oxidation to form chemiluminescing reaction products were analyzed to evaluate the nature of the M(CO)_{rm x } adducts and study MOcdotCO solvation complexes. The study was facilitated by comparing the optical signatures for the chemiluminescent oxidation of rare gas entrained metal atoms. Oxidation processes involving vanadium, chromium, and aluminum complexes were studied. In the case of vanadium, transitions associated with two previously unreported states of vanadium monoxide (VO) were observed and characterized. Transitions which may be associated with a VOcdotCO complex were also observed. For the case of chromium, three previously unreported states of chromium monofluoride (CrF) were characterized. Two band systems, which are tentatively ascribed to Cr_2F, were also observed. For the case of aluminum, the differences in the AlO B state population distribution formed in the Al+CO+O_3 and Al+Ar+O_3 systems provided a means of evaluating the binding energy of the Al(CO)_2 complex. Laser induced fluorescence (LIF) was used to probe the van der Waals complex AlAr formed in a free jet expansion. Based on rotationally resolved B^2Sigma ^{+} >=ts X^2 Pi_{1/2} electronic transitions, definitive interatomic potential parameters were developed for the AlAr B^2Sigma^{+ } state. AlAr X^2Pi_ {1/2} state interatomic potential parameter were developed assuming a Morse potential. Lambda doubling of the X^2Pi_ {1/2} state is evident, consistent with the presence of an unobserved repulsive AlAr A ^2Sigma^{+} state. Finally, the LIF excitation and emission spectra obtained for Fe/Ar and photolyzed Fe(CO)_5 /Ar matrices were compared. Previously unreported transitions associated with matrix-isolated Fe atoms were observed in the range from 500 to 1600 nm. Differences were observed in the spectra characterizing

  4. Bis(allyl)-ruthenium(IV) complexes as highly efficient catalysts for the redox isomerization of allylic alcohols into carbonyl compounds in organic and aqueous media: scope, limitations, and theoretical analysis of the mechanism.

    PubMed

    Cadierno, Victorio; García-Garrido, Sergio E; Gimeno, José; Varela-Alvarez, Adrián; Sordo, José A

    2006-02-01

    The catalytic activity of the bis(allyl)-ruthenium(IV) dimer [[Ru(eta(3):eta(3)-C(10)H(16))(mu-Cl)Cl](2)] (C(10)H(16) = 2,7-dimethylocta-2,6-diene-1,8-diyl) (1), and that of its mononuclear derivatives [Ru(eta(3):eta(3)-C(10)H(16))Cl(2)(L)] (L = CO, PR(3), CNR, NCR) (2) and [Ru(eta(3):eta(3)-C(10)H(16))Cl(NCMe)(2)][SbF(6)] (3), in the redox isomerization of allylic alcohols into carbonyl compounds, both in tetrahydrofuran and in water, is reported. In particular, a variety of allylic alcohols have been quantitatively isomerized using [[Ru(eta(3):eta(3)-C(10)H(16))(mu-Cl)Cl](2)] (1) as catalyst, the reactions proceeding in all cases faster in water. Remarkably, complex 1 has been found to be the most efficient catalyst reported to date for this particular transformation, leading to TOF and TON values up to 62,500 h(-1) and 1 500,000, respectively. Moreover, catalyst 1 can be recycled and is capable of performing allylic alcohol isomerizations even in the presence of conjugated dienes, which are known to be strong poisons in isomerization catalysis. On the basis of both experimental data and theoretical calculations (DFT), a complete catalytic cycle for the isomerization of 2-propen-1-ol into propenal is described. The potential energy surfaces of the cycle have been explored at the B3LYP/6-311 + G(d,p)//B3LYP/6-31G(d,p) + LAN2DZ level. The proposed mechanism involves the coordination of the oxygen atom of the allylic alcohol to the metal. The DFT energy profile is consistent with the experimental observation that the reaction only proceeds under heating. Calculations predict the catalytic cycle to be strongly exergonic, in full agreement with the high yields experimentally observed.

  5. Gas-phase complexes of Ni2+ and Ca2+ with deprotonated histidylhistidine (HisHis): A model case for polyhistidyl-metal binding motifs

    NASA Astrophysics Data System (ADS)

    Peckelsen, Katrin; Martens, Jonathan; Berden, Giel; Oomens, Jos; Dunbar, Robert C.; Meijer, Anthony J. H. M.; Schäfer, Mathias

    2017-02-01

    In the complex formed between the calcium cation (Ca2+) and a deprotonated HisHis dipeptide, the complex adopts a charge solvation (CS) structure. Ca2+, a weak binding main group metal cation, interacts with the oxygens of the peptide carbonyl moiety and the deprotonated C-terminus. In contrast, the much stronger binding Ni2+ cation deprotonates the peptide nitrogen and induces an iminolate (Im) ligand structure in the [Ni(HisHis-H)]+ complex ion. The combination of infrared multiple-photon dissociation (IRMPD) spectroscopy and quantum chemistry evidence these two representative binding motifs. The iminolate coordination pattern identified and characterized in the [Ni(HisHis-H)]+ complex serves as a model case for nickel complexes of poly-histidyl-domains and is thereby also of interest to better understand the fundamentals of immobilized metal ion affinity chromatography as well as of Ni co-factor chemistry in enzymology.

  6. Process and catalyst for carbonylating olefins

    DOEpatents

    Zoeller, J.R.

    1998-06-02

    Disclosed is an improved catalyst system and process for preparing aliphatic carbonyl compounds such as aliphatic carboxylic acids, alkyl esters of aliphatic carboxylic acids and anhydrides of aliphatic carboxylic acids by carbonylating olefins in the presence of a catalyst system comprising (1) a first component selected from at least one Group 6 metal, i.e., chromium, molybdenum, and/or tungsten and (2) a second component selected from at least one of certain halides and tertiary and quaternary compounds of a Group 15 element, i.e., nitrogen, phosphorus and/or arsenic, and (3) as a third component, a polar, aprotic solvent. The process employing the improved catalyst system is carried out under carbonylating conditions of pressure and temperature discussed herein. The process constitutes and improvement over known processes since it can be carried out at moderate carbonylation conditions without the necessity of using an expensive noble metal catalyst, volatile, toxic materials such as nickel tetracarbonyl, formic acid or a formate ester. Further, the addition of a polar, aprotic solvent to the catalyst system significantly increases, or accelerates, the rate at which the carbonylation takes place.

  7. Process and catalyst for carbonylating olefins

    DOEpatents

    Zoeller, Joseph Robert

    1998-06-02

    Disclosed is an improved catalyst system and process for preparing aliphatic carbonyl compounds such as aliphatic carboxylic acids, alkyl esters of aliphatic carboxylic acids and anhydrides of aliphatic carboxylic acids by carbonylating olefins in the presence of a catalyst system comprising (1) a first component selected from at least one Group 6 metal, i.e., chromium, molybdenum, and/or tungsten and (2) a second component selected from at least one of certain halides and tertiary and quaternary compounds of a Group 15 element, i.e., nitrogen, phosphorus and/or arsenic, and (3) as a third component, a polar, aprotic solvent. The process employing the improved catalyst system is carried out under carbonylating conditions of pressure and temperature discussed herein. The process constitutes and improvement over known processes since it can be carried out at moderate carbonylation conditions without the necessity of using an expensive noble metal catalyst, volatile, toxic materials such as nickel tetracarbonyl, formic acid or a formate ester. Further, the addition of a polar, aprotic solvent to the catalyst system significantly increases, or accelerates, the rate at which the carbonylation takes place.

  8. Porphyrins and metal complexes thereof having haloalkyl side chains

    DOEpatents

    Wijesekera, T.; Lyons, J.E.; Ellis, P.E. Jr.; Bhinde, M.V.

    1997-03-04

    Transition metal complexes of meso-haloalkylporphyrins, wherein the haloalkyl groups contain 2 to 8 carbon atoms have been found to be highly effective catalysts for oxidation of alkanes and for the decomposition of hydroperoxides. 7 figs.

  9. Porphyrins and metal complexes thereof having haloalkyl side chains

    DOEpatents

    Wijesekera, Tilak; Lyons, James E.; Ellis, Jr., Paul E.; Bhinde, Manoj V.

    1997-01-01

    Transition metal complexes of meso-haloalkylporphyrins, wherein the haloalkyl groups contain 2 to 8 carbon atoms have been found to be highly effective catalysts for oxidation of alkanes and for the decomposition of hydroperoxides.

  10. N-Heterocyclic carbene metal complexes in medicinal chemistry.

    PubMed

    Oehninger, Luciano; Rubbiani, Riccardo; Ott, Ingo

    2013-03-14

    Metal complexes with N-heterocyclic carbene (NHC) ligands are widely used in chemistry due to their catalytic properties and applied for olefin metathesis among other reactions. The enhanced application of this type of organometallics has over the last few years also triggered a steadily increasing number of studies in the fields of medicinal chemistry, which take advantage of the fascinating chemical properties of these complexes. In fact it has been demonstrated that metal NHC complexes can be used to develop highly efficient metal based drugs with possible applications in the treatment of cancer or infectious diseases. Complexes of silver and gold have been biologically evaluated most frequently but also platinum or other transition metals have demonstrated promising biological properties.

  11. Cooperative reactivity of early-late heterodinuclear transition metal complexes with polar organic substrates

    PubMed

    Gade; Memmler; Kauper; Schneider; Fabre; Bezougli; Lutz; Galka; Scowen; McPartlin

    2000-02-18

    A comprehensive investigation into the cooperative reactivity of two chemically complementary metal-complex fragments in early-late heterodinuclear complexes has been carried out. Reaction of the partially fluorinated tripodal amidozirconium complexes [HC-(SiMe2NR)3Zr(mu-Cl)2Li(OEt2)2] (R = 2-FC6H4: 2a, 2,3,4-F3C6H4: 2b) with K[CpM(CO)2] (M=Fe, Ru) afforded the stable metal-metal bonded heterodinuclear complexes [HC[SiMe2NR]3-Zr-MCp(CO)2] (3-6). Reaction of the dinuclear complexes with methyl isonitrile as well as the heteroallenes CO2, CS2, RNCO and RNCS led to insertion into the polar metal-metal bond. Two of these complexes, [HC[SiMe2N(2-FC6-H4)]3Zr(S2C)Fe(CO)2Cp] (9a) and [HC-[SiMe2N(2-FC2H4)]3Zr-(SCNPh)Fe(CO)2-Cp] (12), have been structurally characterized by a single crystal X-ray structure analysis, proving the structural situation of the inserted substrate as a bridging ligand between the early and late transition metal centre. The reactivity towards organic carbonyl derivatives proved to be varied. Reaction of the heterobimetallic complexes with benzyl and ethylbenzoate led to the cleavage of the ester generating the respective alkoxozirconium complexes [HC[SiMe2N(2-FC6H4)]3ZrOR] (R = Ph-CH2: 13a, Et: 13b) along with [CpFe-[C(O)Ph](CO)2], whereas the analogous reaction with ethyl formate gave 13b along with [CpFeH(CO)2]; this latter complex results from the instability of the formyliron species initially formed. Aryl aldehydes were found to react with the Zr-M complexes according to a Cannizzaro disproportionation pattern yielding the aroyliron and ruthenium complexes along with the respective benzoxyzirconium species. The transfer of the aldehyde hydrogen atom in the course of the reaction was established in a deuteriation experiment. [HC[SiMe2-N(2-FC6H4)]3Zr-M(CO)2Cp] reacted with lactones to give the ring-opened species containing an alkoxozirconium and an acyliron or acylruthenium fragment; the latter binds to the early transition metal centre through

  12. A Simple Method for Drawing Chiral Mononuclear Octahedral Metal Complexes

    ERIC Educational Resources Information Center

    Mohamadou, Aminou; Haudrechy, Arnaud

    2008-01-01

    Octahedral transition-metal complexes are involved in a number of reactions and octahedral coordination geometry, frequently observed for metallic centers, includes important topographical stereochemistry. Depending on the number and nature of different ligands, octahedral coordination units with at least two different monodentate ligands give…

  13. A Simple Method for Drawing Chiral Mononuclear Octahedral Metal Complexes

    ERIC Educational Resources Information Center

    Mohamadou, Aminou; Haudrechy, Arnaud

    2008-01-01

    Octahedral transition-metal complexes are involved in a number of reactions and octahedral coordination geometry, frequently observed for metallic centers, includes important topographical stereochemistry. Depending on the number and nature of different ligands, octahedral coordination units with at least two different monodentate ligands give…

  14. Compartmentation and complexation of metals in hyperaccumulator plants

    PubMed Central

    Leitenmaier, Barbara; Küpper, Hendrik

    2013-01-01

    Hyperaccumulators are being intensely investigated. They are not only interesting in scientific context due to their “strange” behavior in terms of dealing with high concentrations of metals, but also because of their use in phytoremediation and phytomining, for which understanding the mechanisms of hyperaccumulation is crucial. Hyperaccumulators naturally use metal accumulation as a defense against herbivores and pathogens, and therefore deal with accumulated metals in very specific ways of complexation and compartmentation, different from non-hyperaccumulator plants and also non-hyperaccumulated metals. For example, in contrast to non-hyperaccumulators, in hyperaccumulators even the classical phytochelatin-inducing metal, cadmium, is predominantly not bound by such sulfur ligands, but only by weak oxygen ligands. This applies to all hyperaccumulated metals investigated so far, as well as hyperaccumulation of the metalloid arsenic. Stronger ligands, as they have been shown to complex metals in non-hyperaccumulators, are in hyperaccumulators used for transient binding during transport to the storage sites (e.g., nicotianamine) and possibly for export of Cu in Cd/Zn hyperaccumulators [metallothioneins (MTs)]. This confirmed that enhanced active metal transport, and not metal complexation, is the key mechanism of hyperaccumulation. Hyperaccumulators tolerate the high amount of accumulated heavy metals by sequestering them into vacuoles, usually in large storage cells of the epidermis. This is mediated by strongly elevated expression of specific transport proteins in various tissues from metal uptake in the shoots up to the storage sites in the leaf epidermis. However, this mechanism seems to be very metal specific. Non-hyperaccumulated metals in hyperaccumulators seem to be dealt with like in non-hyperaccumulator plants, i.e., detoxified by binding to strong ligands such as MTs. PMID:24065978

  15. Compartmentation and complexation of metals in hyperaccumulator plants.

    PubMed

    Leitenmaier, Barbara; Küpper, Hendrik

    2013-09-20

    Hyperaccumulators are being intensely investigated. They are not only interesting in scientific context due to their "strange" behavior in terms of dealing with high concentrations of metals, but also because of their use in phytoremediation and phytomining, for which understanding the mechanisms of hyperaccumulation is crucial. Hyperaccumulators naturally use metal accumulation as a defense against herbivores and pathogens, and therefore deal with accumulated metals in very specific ways of complexation and compartmentation, different from non-hyperaccumulator plants and also non-hyperaccumulated metals. For example, in contrast to non-hyperaccumulators, in hyperaccumulators even the classical phytochelatin-inducing metal, cadmium, is predominantly not bound by such sulfur ligands, but only by weak oxygen ligands. This applies to all hyperaccumulated metals investigated so far, as well as hyperaccumulation of the metalloid arsenic. Stronger ligands, as they have been shown to complex metals in non-hyperaccumulators, are in hyperaccumulators used for transient binding during transport to the storage sites (e.g., nicotianamine) and possibly for export of Cu in Cd/Zn hyperaccumulators [metallothioneins (MTs)]. This confirmed that enhanced active metal transport, and not metal complexation, is the key mechanism of hyperaccumulation. Hyperaccumulators tolerate the high amount of accumulated heavy metals by sequestering them into vacuoles, usually in large storage cells of the epidermis. This is mediated by strongly elevated expression of specific transport proteins in various tissues from metal uptake in the shoots up to the storage sites in the leaf epidermis. However, this mechanism seems to be very metal specific. Non-hyperaccumulated metals in hyperaccumulators seem to be dealt with like in non-hyperaccumulator plants, i.e., detoxified by binding to strong ligands such as MTs.

  16. Heavy metal music meets complexity and sustainability science.

    PubMed

    Angeler, David G

    2016-01-01

    This paper builds a bridge between heavy metal music, complexity theory and sustainability science to show the potential of the (auditory) arts to inform different aspects of complex systems of people and nature. The links are described along different dimensions. This first dimension focuses on the scientific aspect of heavy metal. It uses complex adaptive systems theory to show that the rapid diversification and evolution of heavy metal into multiple subgenres leads to a self-organizing and resilient socio-musicological system. The second dimension builds on the recent use of heavy metal as a critical thinking model and educational tool, emphasizing the artistic component of heavy metal and its potential to increase people's awareness of environmental sustainability challenges. The relationships between metal, complexity theory and sustainability are first discussed independently to specifically show mechanistic links and the reciprocal potential to inform one domain (science) by the other (metal) within these dimensions. The paper concludes by highlighting that these dimensions entrain each other within a broader social-cultural-environmental system that cannot be explained simply by the sum of independent, individual dimensions. Such a unified view embraces the inherent complexity with which systems of people and nature interact. These lines of exploration suggest that the arts and the sciences form a logical partnership. Such a partnership might help in endeavors to envision, understand and cope with the broad ramifications of sustainability challenges in times of rapid social, cultural, and environmental change.

  17. Protein Carbonylation and Adipocyte Mitochondrial Function*

    PubMed Central

    Curtis, Jessica M.; Hahn, Wendy S.; Stone, Matthew D.; Inda, Jacob J.; Droullard, David J.; Kuzmicic, Jovan P.; Donoghue, Margaret A.; Long, Eric K.; Armien, Anibal G.; Lavandero, Sergio; Arriaga, Edgar; Griffin, Timothy J.; Bernlohr, David A.

    2012-01-01

    Carbonylation is the covalent, non-reversible modification of the side chains of cysteine, histidine, and lysine residues by lipid peroxidation end products such as 4-hydroxy- and 4-oxononenal. In adipose tissue the effects of such modifications are associated with increased oxidative stress and metabolic dysregulation centered on mitochondrial energy metabolism. To address the role of protein carbonylation in the pathogenesis of mitochondrial dysfunction, quantitative proteomics was employed to identify specific targets of carbonylation in GSTA4-silenced or overexpressing 3T3-L1 adipocytes. GSTA4-silenced adipocytes displayed elevated carbonylation of several key mitochondrial proteins including the phosphate carrier protein, NADH dehydrogenase 1α subcomplexes 2 and 3, translocase of inner mitochondrial membrane 50, and valyl-tRNA synthetase. Elevated protein carbonylation is accompanied by diminished complex I activity, impaired respiration, increased superoxide production, and a reduction in membrane potential without changes in mitochondrial number, area, or density. Silencing of the phosphate carrier or NADH dehydrogenase 1α subcomplexes 2 or 3 in 3T3-L1 cells results in decreased basal and maximal respiration. These results suggest that protein carbonylation plays a major instigating role in cytokine-dependent mitochondrial dysfunction and may be linked to the development of insulin resistance in the adipocyte. PMID:22822087

  18. Transition metal complexes of isonicotinic acid (2-hydroxybenzylidene)hydrazide

    NASA Astrophysics Data System (ADS)

    Abou-Melha, Khlood S.

    2008-06-01

    A new series of transition metal complexes of Schiff base isonicotinic acid (2-hydroxybenzylidene)hydrazide, HL, have been synthesized. The Schiff base reacted with Cu(II), Ni(II), Co(II), Mn(II), Fe(III) and UO 2(II) ions as monobasic tridentate ligand to yield mononuclear complexes of 1:2 (metal:ligand) except that of Cu(II) which form complex of 1:1 (metal:ligand). The ligand and its metal complexes were characterized by elemental analyses, IR, UV-vis, mass and 1H NMR spectra, as well as magnetic moment, conductance measurements, and thermal analyses. All complexes have octahedral configurations except Cu(II) complex which has an extra square planar geometry distorted towards tetrahedral. While, the UO 2(II) complex has its favour hepta-coordination. The ligand and its metal complexes were tested against one strain Gram +ve bacteria ( Staphylococcus aureus), Gram -ve bacteria (Escherichia coli) , and Fungi ( Candida albicans). The tested compounds exhibited higher antibacterial activities.

  19. Transition metal complexes of isonicotinic acid (2-hydroxybenzylidene)hydrazide.

    PubMed

    Abou-Melha, Khlood S

    2008-06-01

    A new series of transition metal complexes of Schiff base isonicotinic acid (2-hydroxybenzylidene)hydrazide, HL, have been synthesized. The Schiff base reacted with Cu(II), Ni(II), Co(II), Mn(II), Fe(III) and UO2(II) ions as monobasic tridentate ligand to yield mononuclear complexes of 1:2 (metal:ligand) except that of Cu(II) which form complex of 1:1 (metal:ligand). The ligand and its metal complexes were characterized by elemental analyses, IR, UV-vis, mass and 1H NMR spectra, as well as magnetic moment, conductance measurements, and thermal analyses. All complexes have octahedral configurations except Cu(II) complex which has an extra square planar geometry distorted towards tetrahedral. While, the UO2(II) complex has its favour hepta-coordination. The ligand and its metal complexes were tested against one strain Gram +ve bacteria (Staphylococcus aureus), Gram -ve bacteria (Escherichia coli), and Fungi (Candida albicans). The tested compounds exhibited higher antibacterial activities.

  20. Plant rhamnogalacturonan II complexation of heavy metal cations

    DOEpatents

    O'Neill, Malcolm A.; Pellerin, Patrice J. M.; Warrenfeltz, Dennis; Vidal, Stephane; Darvill, Alan G.; Albersheim, Peter

    1999-01-01

    The present invention provides rhamnogalacturonan-II (RG-II) and relates to its ability to complex specific multivalent heavy metal cations. In the presence of boric acid, RG-II monomers form dimers that are cross-linked by a borate ester. The yield of such borate ester cross-linked dimers of RG-II is enhanced in the presence of specific heavy metal cations. The present invention further relates to the utility of RG-II in assays for the detection of specific heavy metal contamination; as a reagent useful in the removal of specific heavy metal cations contaminating foods and liquids, for example, fish, wines, etc.; as a pharmaceutical composition useful as an antidote in specific heavy metal cation poisoning; as a treatment for the detoxification of specific heavy metal cations from blood and/or tissues; and in a method of remediation of waters and soils contaminated with specific heavy metal cations.

  1. Plant rhamnogalacturonan II complexation of heavy metal cations

    DOEpatents

    O`Neill, M.A.; Pellerin, P.J.M.; Warrenfeltz, D.; Vidal, S.; Darvill, A.G.; Albersheim, P.

    1999-03-02

    The present invention provides rhamnogalacturonan-II (RG-II) and relates to its ability to complex specific multivalent heavy metal cations. In the presence of boric acid, RG-II monomers form dimers that are cross-linked by a borate ester. The yield of such borate ester cross-linked dimers of RG-II is enhanced in the presence of specific heavy metal cations. The present invention further relates to the utility of RG-II in assays for the detection of specific heavy metal contamination; as a reagent useful in the removal of specific heavy metal cations contaminating foods and liquids, for example, fish, wines, etc.; as a pharmaceutical composition useful as an antidote in specific heavy metal cation poisoning; as a treatment for the detoxification of specific heavy metal cations from blood and/or tissues; and in a method of remediation of waters and soils contaminated with specific heavy metal cations. 15 figs.

  2. Preparation of porphyrins and their metal complexes

    DOEpatents

    Ellis, Jr., Paul E.; Langdale, Wayne A.

    1997-01-01

    A hydroxyl-containing pyrrolic compound having a hydroxyl group or a hydroxyl-containing group in the 2-position, optionally substituted in the beta positions, is condensed in an acidified two immiscible phase solvent system to produce excellent yields of the corresponding porphyrin or metal porphyrin.

  3. Preparation of porphyrins and their metal complexes

    DOEpatents

    Ellis, P.E. Jr.; Langdale, W.A.

    1997-08-19

    A hydroxyl-containing pyrrolic compound having a hydroxyl group or a hydroxyl-containing group in the 2-position, optionally substituted in the beta positions, is condensed in an acidified two immiscible phase solvent system to produce excellent yields of the corresponding porphyrin or metal porphyrin.

  4. Aldehydes as alkyl carbanion equivalents for additions to carbonyl compounds

    NASA Astrophysics Data System (ADS)

    Wang, Haining; Dai, Xi-Jie; Li, Chao-Jun

    2016-12-01

    Nucleophilic addition reactions of organometallic reagents to carbonyl compounds for carbon-carbon bond construction have played a pivotal role in modern chemistry. However, this reaction's reliance on petroleum-derived chemical feedstocks and a stoichiometric quantity of metal have prompted the development of many carbanion equivalents and catalytic metal alternatives. Here, we show that naturally occurring carbonyls can be used as latent alkyl carbanion equivalents for additions to carbonyl compounds, via reductive polarity reversal. Such 'umpolung' reactivity is facilitated by a ruthenium catalyst and diphosphine ligand under mild conditions, delivering synthetically valuable secondary and tertiary alcohols in up to 98% yield. The unique chemoselectivity exhibited by carbonyl-derived carbanion equivalents is demonstrated by their tolerance to protic reaction media and good functional group compatibility. Enantioenriched tertiary alcohols can also be accessed with the aid of chiral ligands, albeit with moderate stereocontrol. Such carbonyl-derived carbanion equivalents are anticipated to find broad utility in chemical bond formation.

  5. Aldehydes as alkyl carbanion equivalents for additions to carbonyl compounds

    NASA Astrophysics Data System (ADS)

    Wang, Haining; Dai, Xi-Jie; Li, Chao-Jun

    2017-04-01

    Nucleophilic addition reactions of organometallic reagents to carbonyl compounds for carbon-carbon bond construction have played a pivotal role in modern chemistry. However, this reaction's reliance on petroleum-derived chemical feedstocks and a stoichiometric quantity of metal have prompted the development of many carbanion equivalents and catalytic metal alternatives. Here, we show that naturally occurring carbonyls can be used as latent alkyl carbanion equivalents for additions to carbonyl compounds, via reductive polarity reversal. Such 'umpolung' reactivity is facilitated by a ruthenium catalyst and diphosphine ligand under mild conditions, delivering synthetically valuable secondary and tertiary alcohols in up to 98% yield. The unique chemoselectivity exhibited by carbonyl-derived carbanion equivalents is demonstrated by their tolerance to protic reaction media and good functional group compatibility. Enantioenriched tertiary alcohols can also be accessed with the aid of chiral ligands, albeit with moderate stereocontrol. Such carbonyl-derived carbanion equivalents are anticipated to find broad utility in chemical bond formation.

  6. Metal-metal multiple bonding in C3-symmetric bimetallic complexes of the first row transition metals.

    PubMed

    Krogman, Jeremy P; Thomas, Christine M

    2014-05-25

    Metal-metal multiple bonds have been an intense area of focus in inorganic chemistry for many decades as a result of their fundamentally interesting bonding properties, as well as their potential applications in multielectron transfer and small molecule activation processes. Much of what is known in this field revolves around 2nd and 3rd row transition metals, with fundamental knowledge lacking in the area of bonds between elements of the first transition series. The smaller size and tendency of first row ions to adopt high-spin electron configurations weaken metal-metal interactions and serve to complicate the interpretation of the electronic structure and bonding in bimetallic species containing first row transition metals. Furthermore, traditional tetragonal "paddlewheel" complexes dominate the metal-metal multiple bond literature, and only recently have researchers begun to take advantage of the weaker ligand field in three-fold symmetric bimetallic complexes to encourage more favourable metal-metal bonding interactions. In the past 5 years, several research groups have exploited three-fold symmetric frameworks to investigate new trends in metal-metal bonding involving the first row transition metals. This feature article serves to highlight recent achievements in this area and to use C3-symmetric systems as a model to better understand the fundamental aspects of multiple bonds featuring first row transition metals.

  7. Absorption Spectroscopy, Emissive Properties, and Ultrafast Intersystem Crossing Processes in Transition Metal Complexes: TD-DFT and Spin-Orbit Coupling.

    PubMed

    Daniel, Chantal

    2016-01-01

    Absorption spectroscopy, emissive properties, and ultrafast intersystem crossing processes in transition metal complexes are discussed in the light of recent developments in time-dependent density functional theory (TD-DFT), spin-orbit coupling (SOC) effects, and non-adiabatic excited states dynamics. Methodological highlights focus on spin-orbit and vibronic couplings and on the recent strategies available for simulating ultra-fast intersystem crossings (ISC).The role of SOC in the absorption spectroscopy of third-row transition metal complexes is illustrated by two cases studies, namely Ir(III) phenyl pyridine and Re(I) carbonyl bipyridine complexes.The problem of luminescence decay in third-row transition metal complexes handled by TD-DFT linear and quadratic response theories including SOC is exemplified by three studies: (1) the phosphorescence of Ir(III) complexes from the lowest triplet state; (2) the emissive properties of square planar Pt(II) complexes with bidentate and terdentate ligands characterized by low-lying metal-to-ligand-charge-transfer (MLCT) and metal-centered (MC) states; and (3) the ultra-fast luminescence decay of Re(I) carbonyl bipyridine halides via low-lying singlet and triplet charge transfer states delocalized over the bipyridine and the halide ligands.Ultrafast ISC occurring in spin crossover [Fe (bpy)3]2+, in [Ru (bpy)3]2+, and [Re (Br)(CO)3(bpy] complexes are deciphered thanks to recent developments based on various approaches, namely non-radiative rate theory within the Condon approximation, non-adiabatic surface hopping molecular dynamics, and quantum wave packet dynamics propagation.

  8. Metal complexes of diisopropylthiourea: synthesis, characterization and antibacterial studies.

    PubMed

    Ajibade, Peter A; Zulu, Nonkululeko H

    2011-01-01

    Co(II), Cu(II), Zn(II) and Fe(III) complexes of diisopropylthiourea have been synthesized and characterized by elemental analyses, molar conductivity, magnetic susceptibility, FTIR and electronic spectroscopy. The compounds are non-electrolytes in solution and spectroscopic data of the complexes are consistent with 4-coordinate geometry for the metal(II) complexes and six coordinate octahedral for Fe(III) complex. The complexes were screened for their antibacterial activities against six bacteria: Escherichia coli, Pseudomonas auriginosa, Klebsiella pneumoniae, Bacillus cereus, Staphylococcus aureus and Bacillus pumilus. The complexes showed varied antibacterial activities and their minimum inhibitory concentrations (MICs) were determined.

  9. Metal Complexes of Diisopropylthiourea: Synthesis, Characterization and Antibacterial Studies

    PubMed Central

    Ajibade, Peter A.; Zulu, Nonkululeko H.

    2011-01-01

    Co(II), Cu(II), Zn(II) and Fe(III) complexes of diisopropylthiourea have been synthesized and characterized by elemental analyses, molar conductivity, magnetic susceptibility, FTIR and electronic spectroscopy. The compounds are non-electrolytes in solution and spectroscopic data of the complexes are consistent with 4-coordinate geometry for the metal(II) complexes and six coordinate octahedral for Fe(III) complex. The complexes were screened for their antibacterial activities against six bacteria: Escherichia coli, Pseudomonas auriginosa, Klebsiella pneumoniae, Bacillus cereus, Staphylococcus aureus and Bacillus pumilus. The complexes showed varied antibacterial activities and their minimum inhibitory concentrations (MICs) were determined. PMID:22072941

  10. Carbonyl compounds indoors in a changing climate

    PubMed Central

    2012-01-01

    Background Formic acid, acetic acid and formaldehyde are important compounds in the indoor environment because of the potential for these acids to degrade calcareous materials (shells, eggs, tiles and geological specimens), paper and corrode or tarnish metals, especially copper and lead. Carbonyl sulfide tarnishes both silver and copper encouraging the formation of surface sulfides. Results Carbonyls are evolved more quickly at higher temperatures likely in the Cartoon Gallery at Knole, an important historic house near Sevenoaks in Kent, England where the study is focused. There is a potential for higher concentrations to accumulate. However, it may well be that in warmer climates they will be depleted more rapidly if ventilation increases. Conclusions Carbonyls are likely to have a greater impact in the future. PMID:22439648

  11. Determining the magnitude and direction of photoinduced ligand field switching in photochromic metal-organic complexes: molybdenum-tetracarbonyl spirooxazine complexes.

    PubMed

    Paquette, Michelle M; Patrick, Brian O; Frank, Natia L

    2011-07-06

    The ability to optically switch or tune the intrinsic properties of transition metals (e.g., redox potentials, emission/absorption energies, and spin states) with photochromic metal-ligand complexes is an important strategy for developing "smart" materials. We have described a methodology for using metal-carbonyl complexes as spectroscopic probes of ligand field changes associated with light-induced isomerization of photochromic ligands. Changes in ligand field between the ring-closed spirooxazine (SO) and ring-opened photomerocyanine (PMC) forms of photochromic azahomoadamantyl and indolyl phenanthroline-spirooxazine ligands are demonstrated through FT-IR, (13)C NMR, and computational studies of their molybdenum-tetracarbonyl complexes. The frontier molecular orbitals (MOs) of the SO and PMC forms differ considerably in both electron density distributions and energies. Of the multiple π* MOs in the SO and PMC forms of the ligands, the LUMO+1, a pseudo-b(1)-symmetry phenanthroline-based MO, mixes primarily with the Mo(CO)(4) fragment and provides the major pathway for Mo(d)→phen(π*) backbonding. The LUMO+1 is found to be 0.2-0.3 eV lower in energy in the SO form relative to the PMC form, suggesting that the SO form is a better π-acceptor. Light-induced isomerization of the photochromic ligands was therefore found to lead to changes in the energies of their frontier MOs, which in turn leads to changes in π-acceptor ability and ligand field strength. Ligand field changes associated with photoisomerizable ligands allow tuning of excited-state and ground-state energies that dictate energy/electron transfer, optical/electrical properties, and spin states of a metal center upon photoisomerization, positioning photochromic ligand-metal complexes as promising targets for smart materials.

  12. Metal complexes of substituted Gable porphyrins as oxidation catalysts

    DOEpatents

    Lyons, J.E.; Ellis, P.E. Jr.; Wagner, R.W.

    1996-01-02

    Transition metal complexes of Gable porphyrins are disclosed having two porphyrin rings connected through a linking group, and having on the porphyrin rings electron-withdrawing groups, such as halogen, nitro or cyano. These complexes are useful as catalysts for the oxidation of organic compounds, e.g. alkanes.

  13. Metal complexes of substituted Gable porphyrins as oxidation catalysts

    DOEpatents

    Lyons, James E.; Ellis, Jr., Paul E.; Wagner, Richard W.

    1996-01-01

    Transition metal complexes of Gable porphyrins having two porphyrin rings connected through a linking group, and having on the porphyrin rings electron-withdrawing groups, such as halogen, nitro or cyano. These complexes are useful as catalysts for the oxidation of organic compounds, e.g. alkanes.

  14. An Experiment on Isomerism in Metal-Amino Acid Complexes.

    ERIC Educational Resources Information Center

    Harrison, R. Graeme; Nolan, Kevin B.

    1982-01-01

    Background information, laboratory procedures, and discussion of results are provided for syntheses of cobalt (III) complexes, I-III, illustrating three possible bonding modes of glycine to a metal ion (the complex cations II and III being linkage/geometric isomers). Includes spectrophotometric and potentiometric methods to distinguish among the…

  15. A new metalation complex for organic synthesis and polymerization reactions

    NASA Technical Reports Server (NTRS)

    Hirshfield, S. M.

    1971-01-01

    Organometallic complex of N,N,N',N' tetramethyl ethylene diamine /TMEDA/ and lithium acts as metalation intermediate for controlled systhesis of aromatic organic compounds and polymer formation. Complex of TMEDA and lithium aids in preparation of various organic lithium compounds.

  16. An Experiment on Isomerism in Metal-Amino Acid Complexes.

    ERIC Educational Resources Information Center

    Harrison, R. Graeme; Nolan, Kevin B.

    1982-01-01

    Background information, laboratory procedures, and discussion of results are provided for syntheses of cobalt (III) complexes, I-III, illustrating three possible bonding modes of glycine to a metal ion (the complex cations II and III being linkage/geometric isomers). Includes spectrophotometric and potentiometric methods to distinguish among the…

  17. Complexed metals in hazardous waste: Limitations of conventional chemical oxidation

    SciTech Connect

    Diel, B.N.; Kuchynka, D.J.; Borchert, J.

    1994-12-31

    In the management of hazardous waste, more is known regarding the treatment of metals than about the fixation, destruction and/or immobilization of any other hazardous constituent group. Metals are the only hazardous constituents which cannot be destroyed, and so must be converted to their least soluble and/or reactive form to prevent reentry into the environment. The occurrence of complexed metals, e.g., metallocyanides, and/or chelated metals, e.g., M{center_dot}EDTA in hazardous waste streams presents formidable challenges to conventional waste treatment practices. This paper presents the results of extensive research into the destruction (chemical oxidation) of metallocyanides and metal-chelates, defines the utility and limitations of conventional chemical oxidation approaches, illustrates some of the waste management difficulties presented by such species, and presents preliminary data on the UV/H{sub 2}O{sub 2} photodecomposition of chelated metals.

  18. Low-Molecular-Mass Metal Complexes in the Mouse Brain

    PubMed Central

    McCormick, Sean P.; Chakrabarti, Mrinmoy; Cockrell, Allison L.; Park, Jinkyu; Lindahl, Lora S.; Lindahl, Paul A.

    2013-01-01

    The presence of labile low-molecular-mass (LMM, defined as < 10 kDa) metal complexes in cells and super-cellular structures such as the brain has been inferred from chelation studies, but direct evidence is lacking. To evaluate the presence of LMM metal complexes in the brain, supernatant fractions of fresh mouse brain homogenates were passed through a 10 kDa cutoff membrane and subjected to size-exclusion liquid chromatography under anaerobic refrigerated conditions. Fractions were monitored for Mn, Fe, Co, Cu, Zn, Mo, S and P using an on-line ICP-MS. At least 30 different LMM metal complexes were detected along with numerous P- and S- containing species. Reproducibility was assessed by performing the experiment 13 times, using different buffers, and by examining whether complexes changed with time. Eleven Co, 2 Cu, 5 Mn, 4 Mo, 3 Fe and 2 Zn complexes with molecular masses < 4 kDa were detected. One LMM Mo complex comigrated with the molybdopterin cofactor. Most Cu and Zn complexes appeared to be protein-bound with masses ranging from 4 – 20 kDa. Co was the only metal for which the “free” or aqueous complex was reproducibly observed. Aqueous Co may be sufficiently stable in this environment due to its relatively slow water-exchange kinetics. Attempts were made to assign some of these complexes, but further efforts will be required to identify them unambiguously and to determine their functions. This is among the first studies to detect low-molecular-mass transition metal complexes in the mouse brain using LC-ICP-MS. PMID:23443205

  19. Crystallization experiments with the dinuclear chelate ring complex di-μ-chlorido-bis[(η(2)-2-allyl-4-methoxy-5-{[(propan-2-yloxy)carbonyl]methoxy}phenyl-κC(1))platinum(II)].

    PubMed

    Nguyen Thi Thanh, Chi; Pham Van, Thong; Le Thi Hong, Hai; Van Meervelt, Luc

    2016-10-01

    Crystallization experiments with the dinuclear chelate ring complex di-μ-chlorido-bis[(η(2)-2-allyl-4-methoxy-5-{[(propan-2-yloxy)carbonyl]methoxy}phenyl-κC(1))platinum(II)], [Pt2(C15H19O4)2Cl2], containing a derivative of the natural compound eugenol as ligand, have been performed. Using five different sets of crystallization conditions resulted in four different complexes which can be further used as starting compounds for the synthesis of Pt complexes with promising anticancer activities. In the case of vapour diffusion with the binary chloroform-diethyl ether or methylene chloride-diethyl ether systems, no change of the molecular structure was observed. Using evaporation from acetonitrile (at room temperature), dimethylformamide (DMF, at 313 K) or dimethyl sulfoxide (DMSO, at 313 K), however, resulted in the displacement of a chloride ligand by the solvent, giving, respectively, the mononuclear complexes (acetonitrile-κN)(η(2)-2-allyl-4-methoxy-5-{[(propan-2-yloxy)carbonyl]methoxy}phenyl-κC(1))chloridoplatinum(II) monohydrate, [Pt(C15H19O4)Cl(CH3CN)]·H2O, (η(2)-2-allyl-4-methoxy-5-{[(propan-2-yloxy)carbonyl]methoxy}phenyl-κC(1))chlorido(dimethylformamide-κO)platinum(II), [Pt(C15H19O4)Cl(C2H7NO)], and (η(2)-2-allyl-4-methoxy-5-{[(propan-2-yloxy)carbonyl]methoxy}phenyl-κC(1))chlorido(dimethyl sulfoxide-κS)platinum(II), determined as the analogue {η(2)-2-allyl-4-methoxy-5-[(ethoxycarbonyl)methoxy]phenyl-κC(1)}chlorido(dimethyl sulfoxide-κS)platinum(II), [Pt(C14H17O4)Cl(C2H6OS)]. The crystal structures confirm that acetonitrile interacts with the Pt(II) atom via its N atom, while for DMSO, the S atom is the coordinating atom. For the replacement, the longest of the two Pt-Cl bonds is cleaved, leading to a cis position of the solvent ligand with respect to the allyl group. The crystal packing of the complexes is characterized by dimer formation via C-H...O and C-H...π interactions, but no π-π interactions are observed despite the presence of

  20. Complex Microfiltration Behavior of Metal Hydroxide Slurries

    SciTech Connect

    Shimskey, Rick W.; Schonewill, Philip P.; Daniel, Richard C.; Peterson, Reid A.

    2011-02-28

    Crossflow filtration is to be a key process in the treatment and disposal of approximately 60,000 metric tons of high-level waste stored at the Hanford Site in Richland, Washington. Pacific Northwest National Laboratory is assessing filter performance against waste simulant materials that mimic the chemical and physical properties of Hanford tank waste. Prior simulant studies indicate that waste filtration performance may be limited by pore and cake fouling. To limit the shutdown of waste treatment operations, the pre-treatment facility plans to recover filter flux loses from cake formation and filter fouling by frequently backpulsing the filter elements. The objective of the current research is to develop an understanding of the roles of cake and pore fouling and potential flux recovery through backpulsing of the filters for Hanford waste filtration operations. Metal hydroxide wastes were tested to examine the role of particle-filter interaction on filter performance.

  1. Pyridylphosphinate metal complexes: synthesis, structural characterisation and biological activity.

    PubMed

    Cross, Jasmine M; Gallagher, Natalie; Gill, Jason H; Jain, Mohit; McNeillis, Archibald W; Rockley, Kimberly L; Tscherny, Fiona H; Wirszycz, Natasha J; Yufit, Dmitry S; Walton, James W

    2016-08-09

    For the first time, a series of 25 pseudo-octahedral pyridylphosphinate metal complexes (Ru, Os, Rh, Ir) has been synthesised and assessed in biological systems. Each metal complex incorporates a pyridylphosphinate ligand, a monodentate halide and a capping η(6)-bound aromatic ligand. Solid- and solution-state analyses of two complexes reveal a structural preference for one of a possible two diastereomers. The metal chlorides hydrolyse rapidly in D2O to form a 1 : 1 equilibrium ratio between the aqua and chloride adducts. The pKa of the aqua adduct depends upon the pyridyl substituent and the metal but has little dependence upon the phosphinate R' group. Toxicity was measured in vitro against non-small cell lung carcinoma H460 cells, with the most potent complexes reporting IC50 values around 50 μM. Binding studies with selected amino acids and nucleobases provide a rationale for the variation in toxicity observed within the series. Finally, an investigation into the ability of the chelating amino acid l-His to displace the phosphinate O-metal bond shows the potential for phosphinate complexes to act as prodrugs that can be activated in the intracellular environment.

  2. Preparation of nanoporous metal foam from high nitrogen transition metal complexes

    DOEpatents

    Tappan, Bryce C.; Huynh, My Hang V.; Hiskey, Michael A.; Son, Steven F.; Oschwald, David M.; Chavez, David E.; Naud, Darren L.

    2006-11-28

    Nanoporous metal foams are prepared by ignition of high nitrogen transition metal complexes. The ammonium salts of iron(III) tris[bi(tetrazolato)-amine], cobalt(III) tris(bi(tetrazolato)amine), and high nitrogen compounds of copper and silver were prepared as loose powders, pressed into pellets and wafers, and ignited under an inert atmosphere to form nanoporous metal foam monoliths having very high surface area and very low density.

  3. Synthesis and chemistry of yttrium and lanthanide metal complexes

    SciTech Connect

    Evans, W.J.

    1991-09-01

    The objective of this research project is to determine the special features of complexes of yttrium and the lanthanide metals which will allow the design and synthesis of materials with unique chemical, physical, and catalytic properties. Past studies of yttrium and lanthanide metal alkyl and hydride complexes stabilized by cyclopentadienyl co-ligands have shown that a substantial, often singular, organometallic chemistry is available via these metals. More extensive utilization of the chemical opportunities available through yttrium and the lanthanides would be possible, however, if stabilizing ancillary ligand systems less sensitive to oxidation and protonolysis than cyclopentadienides could be developed. Alkoxide ligands are attractive in this regard and our recent research had focused on alkoxides and the special opportunities they can provide to these metals. 6 refs., 10 figs.

  4. Magnetite-sulfide-metal complexes in the Allende meteorite

    NASA Technical Reports Server (NTRS)

    Haggerty, S. E.; Mcmahon, B. M.

    1979-01-01

    A model of liquid immiscibility is presented that seemingly accounts for the sulfide-oxide-metal complexes that are present in olivine-rich chondrules in the Allende meteorite. The four major assemblages that are identified are: (1) magnetite + Ni-Fe metal; (2) magnetite + troilite + Ni-Fe metal; (3) magnetite + troilite + pentlandite + Ni-Fe metal; and (4) troilite + or - pentlandite. Specific attention is focused on oxide-metal associations and experimental data confirm earlier suggestions that magnetite results from the oxidation of an initially high-Fe-content metal alloy. Oxidation decreases the modal abundance of the Fe metal and this is accompanied by substantial increases in Ni contents which reach a maximum of approximately 70 wt % Ni. The proposed oxidation mechanism is entirely consistent with condensation of Fe-metal + olivine (Fa5) that subsequently reequilibrated at lower temperatures. Although the sulfide constituents could also have formed by the reaction of Fe-Ni metal + gaseous H2S, sulfide immiscibility under increased conditions of partial O2 pressure is the preferred process.

  5. The photochemistry of transition metal complexes using density functional theory.

    PubMed

    Garino, Claudio; Salassa, Luca

    2013-07-28

    The use of density functional theory (DFT) and time-dependent DFT (TD-DFT) to study the photochemistry of metal complexes is becoming increasingly important among chemists. Computational methods provide unique information on the electronic nature of excited states and their atomic structure, integrating spectroscopy observations on transient species and excited-state dynamics. In this contribution, we present an overview on photochemically active transition metal complexes investigated by DFT. In particular, we discuss a representative range of systems studied up to now, which include CO- and NO-releasing inorganic and organometallic complexes, haem and haem-like complexes dissociating small diatomic molecules, photoactive anti-cancer Pt and Ru complexes, Ru polypyridyls and diphosphino Pt derivatives.

  6. Photochemical route to actinide-transition metal bonds: synthesis, characterization and reactivity of a series of thorium and uranium heterobimetallic complexes

    SciTech Connect

    Ward, Ashleigh; Lukens, Wayne; Lu, Connie; Arnold, John

    2014-04-01

    A series of actinide-transition metal heterobimetallics has been prepared, featuring thorium, uranium and cobalt. Complexes incorporating the binucleating ligand N[-(NHCH2PiPr2)C6H4]3 and Th(IV) (4) or U(IV) (5) with a carbonyl bridged [Co(CO)4]- unit were synthesized from the corresponding actinide chlorides (Th: 2; U: 3) and Na[Co(CO)4]. Irradiation of the isocarbonyls with ultraviolet light resulted in the formation of new species containing actinide-metal bonds in good yields (Th: 6; U: 7); this photolysis method provides a new approach to a relatively rare class of complexes. Characterization by single-crystal X-ray diffraction revealed that elimination of the bridging carbonyl is accompanied by coordination of a phosphine arm from the N4P3 ligand to the cobalt center. Additionally, actinide-cobalt bonds of 3.0771(5) and 3.0319(7) for the thorium and uranium complexes, respectively, were observed. The solution state behavior of the thorium complexes was evaluated using 1H, 1H-1H COSY, 31P and variable-temperature NMR spectroscopy. IR, UV-Vis/NIR, and variable-temperature magnetic susceptibility measurements are also reported.

  7. Metal Complexes of EDTA: An Exercise in Data Interpretation

    NASA Astrophysics Data System (ADS)

    Mitchell, Philip C. H.

    1997-10-01

    Stability constants of metal complexes of edta with main group and transition metals are correlated with properties of the elements and cations (ion charge, atomic and ionic radii, ionization energies and electronegativities) and interpreted with an ionic bonding model including a covalent contribution. Enthalpy and entropy contributions are discussed. It is shown how chemists recognize patterns in data with the help of a general theory and so develop a model.

  8. Electrochemical response of metal complexes in homogeneous solution under photoirradiation

    NASA Astrophysics Data System (ADS)

    Fukatsu, Arisa; Kondo, Mio; Okamura, Masaya; Yoshida, Masaki; Masaoka, Shigeyuki

    2014-06-01

    The electrochemical detection of metal complexes in the photoexcited state is important for understanding photoinduced electron transfer (PET) processes, which play a central role in photo-energy conversion systems. In general, however, the redox potentials of excited states have been indirectly estimated by a combination of spectroscopic properties and ground-state redox potentials. To establish a simple method for directly determining the redox potentials of the photoexcited states of metal complexes, electrochemical measurements under several conditions were performed. The electrochemical response was largely influenced not only by the generation of photoexcited molecules but also by the convection induced by photoirradiation, even when the global temperature of the sample solution was unchanged. The suppression of these unfavourable electrochemical responses was successfully achieved by adopting well-established electrochemical techniques. Furthermore, as an initial demonstration, the photoexcited state of a Ru-based metal complex was directly detected, and its redox potential was determined using a thin layer electrochemical method.

  9. An efficient fluctuating charge model for transition metal complexes.

    PubMed

    Comba, Peter; Martin, Bodo; Sanyal, Avik

    2013-07-05

    A fluctuating charge model for transition metal complexes, based on the Hirshfeld partitioning scheme, spectroscopic energy data from the NIST Atomic Spectroscopy Database and the electronegativity equalization approach, has been developed and parameterized for organic ligands and their high- and low-spin Fe(II) and Fe(III), low-spin Co(III) and Cu(II) complexes, using atom types defined in the Momec force field. Based on large training sets comprising a variety of transition metal complexes, a general parameter set has been developed and independently validated which allows the efficient computation of geometry-dependent charge distributions in the field of transition metal coordination compounds. Copyright © 2013 Wiley Periodicals, Inc.

  10. DFT, characterization and investigation of vibrational spectroscopy of 4-(4-hydroxy)-3-(2-pyrazine-2-carbonyl)hydrazonomethylphenyl-diazen-yl-benzenesulfonamide and its copper(II) complex

    NASA Astrophysics Data System (ADS)

    Ammar, Reda A. A.; Alaghaz, Abdel-Nasser M. A.; Elhenawy, Ahmed A.

    2014-06-01

    Azo-Schiff-base complex of Cu(II) has been synthesized and characterized by elemental, spectral and thermal studies. The conductance data indicate the non-electrolytic nature of the complex. The IR spectra of the prepared complex was suggested that the azo-Schiff-base ligand [4-(4-hydroxy)-3-(2-pyrazine-2-carbonyl)hydrazonomethylphenyl-diazen-yl-benzenesulfonamide] (H2L) behaves as a tri-dentate ligand through the carbonyl oxygen atom, azomethine nitrogen atom and phenolic oxygen atom (ONO). The surface morphology (SEM) of the ligand and its copper(II) complex was studied using SEM analysis. X-ray powder diffraction (XRD) helps to determine the cell parameters of the complex. Transmission electron microscopy (TEM) indicated spherical particles of ∼200 nm diameter. The physico-chemical studies revealed octahedral geometry around copper ion. The EPR spectra of copper complex in DMSO at 300 and 77 K were recorded and their salient feature was reported. The redox behavior of the ligand and its copper(II) complex were studied using cyclic voltammetry. Thermal properties and decomposition kinetics of copper(II) complex was investigated. The interpretation mathematical analysis and evaluation of kinetic parameters (E, A, ΔH, ΔS and ΔG) of all thermal decomposition stages have been evaluated using Coats-Redfern (CR), Horowitz-Metzger (HM) and Piloyan-Novikova (PN) equations. Moreover, the density functional theory studies are discussed for ligand, using DFT/B3LYP with 6-31G* and 6-311G* level of theory, the absorption spectra has been computed by using time dependent at TD-DFT/B3LYP with 6-31G* and 6-311G* level of theory. The HOMO-LUMO energy gap of studied systems has been discussed.

  11. Vacuum filling of complex microchannels with liquid metal.

    PubMed

    Lin, Yiliang; Gordon, Olivia; Khan, M Rashed; Vasquez, Neyanel; Genzer, Jan; Dickey, Michael D

    2017-09-12

    This paper describes the utilization of vacuum to fill complex microchannels with liquid metal. Microchannels filled with liquid metal are useful as conductors for soft and stretchable electronics, as well as for microfluidic components such as electrodes, antennas, pumps, or heaters. Liquid metals are often injected manually into the inlet of a microchannel using a syringe. Injection can only occur if displaced air in the channels has a pathway to escape, which is usually accomplished using outlets. The positive pressure (relative to atmosphere) needed to inject fluids can also cause leaks or delamination of the channels during injection. Here we show a simple and hands-free method to fill microchannels with liquid metal that addresses these issues. The process begins by covering a single inlet with liquid metal. Placing the entire structure in a vacuum chamber removes the air from the channels and the surrounding elastomer. Restoring atmospheric pressure in the chamber creates a positive pressure differential that pushes the metal into the channels. Experiments and a simple model of the filling process both suggest that the elastomeric channel walls absorb residual air displaced by the metal as it fills the channels. Thus, the metal can fill dead-ends with features as small as several microns and branched structures within seconds without the need for any outlets. The method can also fill completely serpentine microchannels up to a few meters in length. The ability to fill dense and complex geometries with liquid metal in this manner may enable broader application of liquid metals in electronic and microfluidic applications.

  12. Enantioselective Iridium-Catalyzed Carbonyl Allylation from the Alcohol or Aldehyde Oxidation Level Using Allyl Acetate as an Allyl Metal Surrogate

    PubMed Central

    Kim, In Su; Ngai, Ming-Yu; Krische, Michael J.

    2010-01-01

    A method for carbonyl allylation and crotylation from the alcohol oxidation state via allyl acetate-alcohol transfer hydrogenative C-C coupling is described. Exposure of allyl acetate to benzylic and allylic alcohols 1a-9a in the presence of an iridium catalyst derived from [IrCl(cod)]2 and BIPHEP delivers products of C-allylation 1b-9b. Similarly, 3-acetoxy-1-butene couples to allylic alcohols 1a-9a to furnish crotylation products 1c-9c. The ability of this allylation protocol to transcend the boundaries imposed by oxidation level are demonstrated by the coupling of allyl acetate to aldehydes 1d-3d under standard conditions, but employing isopropanol as terminal reductant. The products of C-allylation 1b-3b are obtained in isolated yields comparable to those obtained in the corresponding alcohol coupling reactions. These studies contribute to a paradigm shift in carbonyl addition chemistry that defines a departure from preformed organometallic reagents. PMID:18444616

  13. Luminescent molecular rods - transition-metal alkynyl complexes.

    PubMed

    Yam, Vivian Wing-Wah; Wong, Keith Man-Chung

    2005-01-01

    A number of transition-metal complexes have been reported to exhibit rich luminescence, usually originating from phosphorescence. Such luminescence properties of the triplet excited state with a large Stoke's shift, long lifetime, high luminescence quantum yield as well as lower excitation energy, are envisaged to serve as an ideal candidate in the area of potential applications for chemosensors, dye-sensitized solar cells, flat panel displays, optics, new materials and biological sciences. Organic alkynes (poly-ynes), with extended or conjugatedπ-systems and rigid structure with linear geometry, have become a significant research area due to their novel electronic and physical properties and their potential applications in nanotechnology. Owing to the presence of unsaturated sp-hybridized carbon atoms, the alkynyl unit can serve as a versatile building block in the construction of alkynyl transition-metal complexes, not only throughσ-bonding but also viaπ-bonding interactions. By incorporation of linear alkynyl groups into luminescent transition-metal complexes, the alkynyl moiety with goodσ-donor,π-donor andπ-acceptor abilities is envisaged to tune or perturb the emission behaviors, including emission energy (color), intensity and lifetime by its role as an auxiliary ligand as well as to govern the emission origin from its direct involvement. This review summarizes recent efforts on the synthesis of luminescent rod-like alkynyl complexes with different classes of transition metals and details the effects of the introduction of alkynyl groups on the luminescence properties of the complexes.

  14. Properties- and applications of quasicrystals and complex metallic alloys.

    PubMed

    Dubois, Jean-Marie

    2012-10-21

    This article aims at an account of what is known about the potential for applications of quasicrystals and related compounds, the so-called family of Complex Metallic Alloys (CMAs‡). Attention is focused at aluminium-based CMAs, which comprise a large number of crystalline compounds and quasicrystals made of aluminium alloyed with transition metals (like Fe or Cu) or normal metals like Mg. Depending on composition, the structural complexity varies from a few atoms per unit cell up to thousands of atoms. Quasicrystals appear then as CMAs of ultimate complexity and exhibit a lattice that shows no periodicity anymore in the usual 3-dimensional space. Properties change dramatically with lattice complexity and turn the metal-type behaviour of simple Al-based crystals into a far more complex behaviour, with a fingerprint of semi-conductors that may be exploited in various applications, potential or realised. An account of the ones known to the author is given in the light of the relevant properties, namely light absorption, reduced adhesion and friction, heat insulation, reinforcement of composites for mechanical devices, and few more exotic ones. The role played by the search for applications of quasicrystals in the development of the field is briefly addressed in the concluding section.

  15. Metal ion adsorption to complexes of humic acid and metal oxides: Deviations from the additivity rule

    SciTech Connect

    Vermeer, A.W.P.; McCulloch, J.K.; Van Riemsdijk, W.H.; Koopal, L.K.

    1999-11-01

    The adsorption of cadmium ions to a mixture of Aldrich humic acid and hematite is investigated. The actual adsorption to the humic acid-hematite complex is compared with the sum of the cadmium ion adsorptivities to each of the isolated components. It is shown that the sum of the cadmium ion adsorptivities is not equal to the adsorption to the complex. In general, the adsorption of a specific metal ion to the complex can be understood and qualitatively predicted using the adsorptivities to each of the pure components and taking into account the effect of the pH on the interaction between humic acid and iron oxide on the metal ion adsorption. Due to the interaction between the negatively charged humic acid and the positively charged iron oxide, the adsorption of metal ions on the mineral oxide in the complex will increase as compared to that on the isolated oxide, whereas the adsorption to the humic acid will decrease as compared to that on the isolated humic acid. As a result, the overall adsorption of a specific metal ion to the complex will be smaller than predicted by the additivity rule when this metal ion has a more pronounced affinity for the humic acid than for the mineral oxide, whereas it will be larger than predicted by the additivity rule when the metal ion has a higher affinity for the oxide than for the humic acid.

  16. Dinuclear transition metal complexes in carbon nanostructured materials synthesis

    NASA Astrophysics Data System (ADS)

    Ayuso, J. I.; Hernández, E.; Delgado, E.

    2013-06-01

    Carbon nanomaterials (CNMs) were prepared with two similar techniques using organometallic complexes as catalysts precursors. Chemical vapour deposition (CVD) and pyrolysis with chlorine gas approaches were employed in order to explore the effect of dinuclear transition metal compounds [Fe2(CO)6(μ-S2C6H2X2), (X=OH, Cl)] in synthesis of CNMs. Our to-date results have shown these complexes generate different carbonaceous materials when they are used in bulk, it was also observed that their performances in synthesis differ even though these compounds are analogous. With X=OH complex used in CVD process, metal nanoparticles of ca. 20-50 nm in size and embedded in carbon matrix were obtained. X=C1 complex has been used in pyrolysis experiments and showed an entire volatilisation or no reaction, depending on selected temperature. Furthermore, obtaining of a new tetranuclear iron cluster is presented in this work.

  17. Synthesis, spectroscopic characterization, electrochemistry and biological evaluation of some binuclear transition metal complexes of bicompartmental ONO donor ligands containing benzo[b]thiophene moiety

    NASA Astrophysics Data System (ADS)

    Mahendra Raj, K.; Vivekanand, B.; Nagesh, G. Y.; Mruthyunjayaswamy, B. H. M.

    2014-02-01

    A series of new binucleating Cu(II), Co(II), Ni(II) and Zn(II) complexes of bicompartmental ligands with ONO donor were synthesized. The ligands were obtained by the condensation of 3-chloro-6-substituted benzo[b]thiophene-2-carbohydrazides and 4,6-diacetylresorcinol. The synthesized ligands and their complexes were characterized by elemental analysis and various spectroscopic techniques. Elemental analysis, IR, 1H NMR, ESI-mass, UV-Visible, TG-DTA, magnetic measurements, molar conductance and powder-XRD data has been used to elucidate their structures. The bonding sites are the oxygen atom of amide carbonyl, azomethine nitrogen and phenolic oxygen for ligands 1 and 2. The binuclear nature of the complexes was confirmed by ESR spectral data. TG-DTA studies for some complexes showed the presence of coordinated water molecules and the final product is the metal oxide. All the complexes were investigated for their electrochemical activity, only the Cu(II) complexes showed the redox property. Cu(II) complexes were square planar, whereas Co(II), Ni(II) and Zn(II) complexes were octahedral. Powder-XRD pattern have been studied in order to test the degree of crystallinity of the complexes and unit cell calculations were made. In order to evaluate the effect of antimicrobial activity of metal ions upon chelation, both the ligands and their metal complexes were screened for their antibacterial and antifungal activities by minimum inhibitory concentration (MIC) method. The results showed that the metal complexes were found to be more active than free ligands. The DNA cleaving capacities of all the complexes were analyzed by agarose gel electrophoresis method against supercoiled plasmid DNA. Among the compounds tested for antioxidant capacity, ligand 1 displayed excellent activity than its metal complexes.

  18. Anticancer Activity of Metal Complexes: Involvement of Redox Processes

    PubMed Central

    Jungwirth, Ute; Kowol, Christian R.; Keppler, Bernhard K.; Hartinger, Christian G.; Berger, Walter; Heffeter, Petra

    2012-01-01

    Cells require tight regulation of the intracellular redox balance and consequently of reactive oxygen species for proper redox signaling and maintenance of metal (e.g., of iron and copper) homeostasis. In several diseases, including cancer, this balance is disturbed. Therefore, anticancer drugs targeting the redox systems, for example, glutathione and thioredoxin, have entered focus of interest. Anticancer metal complexes (platinum, gold, arsenic, ruthenium, rhodium, copper, vanadium, cobalt, manganese, gadolinium, and molybdenum) have been shown to strongly interact with or even disturb cellular redox homeostasis. In this context, especially the hypothesis of “activation by reduction” as well as the “hard and soft acids and bases” theory with respect to coordination of metal ions to cellular ligands represent important concepts to understand the molecular modes of action of anticancer metal drugs. The aim of this review is to highlight specific interactions of metal-based anticancer drugs with the cellular redox homeostasis and to explain this behavior by considering chemical properties of the respective anticancer metal complexes currently either in (pre)clinical development or in daily clinical routine in oncology. PMID:21275772

  19. Interactions of platinum metals and their complexes in biological systems.

    PubMed Central

    LeRoy, A F

    1975-01-01

    Platinum-metal oxidation catalysts are to be introduced in exhaust systems of many 1975 model-year automobiles in the U.S. to meet Clean Air Act standards. Small quantities of finely divided catalyst have been found issuing from prototype systems; platinum and palladium compounds may be found also. Although platinum exhibits a remarkable resistance to oxidation and chemical attack, it reacts chemically under some conditions producing coordination complex compounds. Palladium reacts more readily than platinum. Some platinum-metal complexes interact with biological systems as bacteriostatic, bacteriocidal, viricidal, and immunosuppressive agents. Workers chronically exposed to platinum complexes often develop asthma-like respiratory distress and skin reactions called platinosis. Platinum complexes used alone and in combination therapy with other drugs have recently emerged as effective agents in cancer chemotherapy. Understanding toxic and favorable interactions of metal species with living organisms requires basic information on quantities and chemical characteristics of complexes at trace concentrations in biological materials. Some basic chemical kinetic and thermodynamic data are presented to characterize the chemical behavior of the complex cis-[Pt(NH3)2Cl2] used therapeutically. A brief discussion of platinum at manogram levels in biological tissue is discussed. PMID:50943

  20. Interactions of platinum metals and their complexes in biological systems.

    PubMed

    LeRoy, A F

    1975-04-01

    Platinum-metal oxidation catalysts are to be introduced in exhaust systems of many 1975 model-year automobiles in the U.S. to meet Clean Air Act standards. Small quantities of finely divided catalyst have been found issuing from prototype systems; platinum and palladium compounds may be found also. Although platinum exhibits a remarkable resistance to oxidation and chemical attack, it reacts chemically under some conditions producing coordination complex compounds. Palladium reacts more readily than platinum. Some platinum-metal complexes interact with biological systems as bacteriostatic, bacteriocidal, viricidal, and immunosuppressive agents. Workers chronically exposed to platinum complexes often develop asthma-like respiratory distress and skin reactions called platinosis. Platinum complexes used alone and in combination therapy with other drugs have recently emerged as effective agents in cancer chemotherapy. Understanding toxic and favorable interactions of metal species with living organisms requires basic information on quantities and chemical characteristics of complexes at trace concentrations in biological materials. Some basic chemical kinetic and thermodynamic data are presented to characterize the chemical behavior of the complex cis-[Pt(NH3)2Cl2] used therapeutically. A brief discussion of platinum at manogram levels in biological tissue is discussed.

  1. Synthesis and characterization of norfloxacin-transition metal complexes (group 11, IB): Spectroscopic, thermal, kinetic measurements and biological activity

    NASA Astrophysics Data System (ADS)

    Refat, Moamen S.

    2007-12-01

    The investigation of the new structures of Ag(I), Cu(II) and Au(III) complexes, [Ag 2(Nor) 2](NO 3) 2, [Cu(Nor) 2(H 2O) 2]SO 4·5H 2O and [Au(Nor) 2 (H 2O) 2]Cl 3 (where, Nor = norfloxacin) was done during the reaction of silver(I), copper(II) and gold(III) ions with norfloxacin drug ligand. Elemental analysis of CHN, infrared, electronic, 1H NMR and mass spectra, as well as thermo gravimetric analysis (TG and DTG) and conductivity measurements have been used to characterize the isolated complexes. The powder XRD studies confirm the amorphous nature of the complexes. The norfloxacin ligand is coordinated to Ag(I) and Au(III) ions as a neutral monodentate chelating through the N atom of piperidyl ring, but the copper(II) complex is coordinated through the carbonyl oxygen atom (quinolone group) and the oxygen atom of the carboxylic group. The norfloxacin and their metal complexes have been biologically tested, which resulted in norfloxacin complexes showing moderate activity against the gram positive and gram negative bacteria as well as against fungi.

  2. Structural Properties and UV-Visible Absorption Spectroscopy of Retinal-pyridyl-CN Re(I) Carbonyl Bipyridine Complex: A Theoretical Study.

    PubMed

    Eng, Julien; Daniel, Chantal

    2015-10-29

    The structural, electronic, and optical properties of the all-trans and five cis conformers of [Re(CO)3(bpy)(ret-pyr-CN)](+) (bpy = 2,2'-bipyridine; ret-pyr-CN = pyridyl-CN-3,7-dimethyl-9-(2,6,6-trimethylcyclohex-2-n)-none-(2,4,6,8-tetraen) were studied in solvent by means of density functional theory (DFT) and time-dependent DFT. The isolated retinal-like chromophore ret-pyr-CN was investigated as well for comparison. By coordination to the complex the two lowest intraligand (IL) states localized on the retinal group are slightly red-shifted from 627 to 690 nm and from 415 to 450 nm, respectively. Several isomerization pathways are open upon irradiation of the Re(I) complex by visible light (400-450 nm), especially to two cis conformers corresponding to the isomerization of the two double bonds of the retinal-like ligand close to the pyridyl group linked to the Re(I) fragment. The metal-to-ligand charge transfer states localized either on the retinal group or on the bpy ligand should play a minor role in the isomerization process itself but could improve its efficiency via ultra-fast intersystem crossing.

  3. Computer simulation of supramolecular assembly by metal-ligand complexation

    NASA Astrophysics Data System (ADS)

    Wang, Shihu; Chen, Chun-Chung; Dormidontova, Elena E.

    2006-03-01

    Monte Carlo simulations were employed to study the supramolecular assembly of oligomers end-functionalized by ligands capable of complexation with metal ions. The properties of these metallo-supramolecular polymers strongly depend on the oligomer concentration, strength of complexation, and metal-to- ligand ratio. At high oligomer concentration the average molecular weight exhibits a maximum near the stoichiometric composition and decreases for higher or lower metal content. On the other hand, at low oligomer concentration the molecular weight shows a local minimum around the stoichiometric composition. This unusual behavior is attributed to the larger population of small rings around the stoichiometric composition, which make up a significant fraction of the overall molecular weight at low oligomer concentration. This effect is especially pronounced at low temperature, where the fraction of rings is higher. The fraction of chains and rings for different concentrations, temperatures and oligomer lengths were calculated and compared with experimental data.

  4. Method for synthesizing metal bis(borano) hypophosphite complexes

    DOEpatents

    Cordaro, Joseph G.

    2013-06-18

    The present invention describes the synthesis of a family of metal bis(borano) hypophosphite complexes. One procedure described in detail is the syntheses of complexes beginning from phosphorus trichloride and sodium borohydride. Temperature, solvent, concentration, and atmosphere are all critical to ensure product formation. In the case of sodium bis(borano) hypophosphite, hydrogen gas was evolved upon heating at temperatures above 150.degree. C. Included in this family of materials are the salts of the alkali metals Li, Na and K, and those of the alkaline earth metals Mg and Ca. Hydrogen storage materials are possible. In particular the lithium salt, Li[PH.sub.2(BH.sub.3).sub.2], theoretically would contain nearly 12 wt % hydrogen. Analytical data for product characterization and thermal properties are given.

  5. Rare earth metal oxazoline complexes in asymmetric catalysis.

    PubMed

    Ward, Benjamin D; Gade, Lutz H

    2012-11-07

    Polydentate oxazolines have been employed as highly effective stereodirecting ligands for asymmetric catalysis with metals from across most of the periodic table. Despite their highly versatile coordination chemistry, the use of these ligands tends to be polarised towards late transition metals; their use with early transition metals and the f-elements is significantly less developed. This current article aims to review the coordination chemistry and catalytic applications of Group 3 and lanthanide complexes supported by ligands possessing oxazoline moieties. Oxazoline-containing ligands were first employed in molecular lanthanide catalysis as early as 1997, yet there is still a significant void in the chemical literature in this respect. The ligands generally employed include bis(oxazolinyl)methane ("BOX"), 2,6-bis(oxazolinyl)pyridine ("pybox"), 1,1,1-tris(oxazolinyl)ethane ("trisox"), and others. The complexes are employed in a wide-range of catalytic applications, especially in Lewis acid catalysis, but also in the stereospecific polymerisation of olefins.

  6. [Applications of metal ions and their complexes in medicine I].

    PubMed

    Nagy, László; Csintalan, Gabriella; Kálmán, Eszter; Sipos, Pál; Szvetnik, Attila

    2003-01-01

    The "inorganic medical chemistry" is a rapidly developing field with enormous potential for applications, which offers new possibilities to the pharmaceutical industry. For example, the titanocene dichloride is already in clinical use, and antimetastatic activity of a range of Ru(III) complexes is also well established. There are ways to minimize the toxicity of Gd(III) complexes and therefore they can be safely injected as MRI contrast agents. The so called "ligand design" allows paramagnetic ions to be targeted to specific organs. Such designed ligands also enable the targeting of radiodiagnostic (99mTc) and radiotherapeutic (186Re) isotopes. There is a significant progress in understanding the coordination chemistry and biochemistry of metal ion(s) containing complexes such as Au antiarthritic and Bi antiulcer drugs. Further, currently developing areas include Mn (SOD mimics), V (insulin mimics), Ru (NO scavengers), Ln-based photosensitizers, metal-targeted organic agents and the Fe overload. The expanding knowledge of the role of metals in biochemistry is expected to provide scope for the design of new drugs in many other areas too, for example neuropharmaceutical and antiaffective agents. Progress in coordination chemistry is strongly dependent on understanding not only the thermodynamics of reactions, but also the kinetics of metal complexes under biologically relevant conditions.

  7. Control of cerium oxidation state through metal complex secondary structures

    SciTech Connect

    Levin, Jessica R.; Dorfner, Walter L.; Carroll, Patrick J.; Schelter, Eric J.

    2015-08-11

    A series of alkali metal cerium diphenylhydrazido complexes, Mx(py)y[Ce(PhNNPh)4], M = Li, Na, and K, x = 4 (Li and Na) or 5 (K), and y = 4 (Li), 8 (Na), or 7 (K), were synthesized to probe how a secondary coordination sphere would modulate electronic structures at a cerium cation. The resulting electronic structures of the heterobimetallic cerium diphenylhydrazido complexes were found to be strongly dependent on the identity of the alkali metal cations. When M = Li+ or Na+, the cerium(III) starting material was oxidized with concomitant reduction of 1,2-diphenylhydrazine to aniline. Reduction of 1,2-diphenylhydrazine was not observed when M = K+, and the complex remained in the cerium(III) oxidation state. Oxidation of the cerium(III) diphenylhydrazido complex to the Ce(IV) diphenylhydrazido one was achieved through a simple cation exchange reaction of the alkali metals. As a result, UV-Vis spectroscopy, FTIR spectroscopy, electrochemistry, magnetic susceptibility, and DFT studies were used to probe the oxidation state and the electronic changes that occurred at the metal centre.

  8. Control of cerium oxidation state through metal complex secondary structures

    DOE PAGES

    Levin, Jessica R.; Dorfner, Walter L.; Carroll, Patrick J.; ...

    2015-08-11

    A series of alkali metal cerium diphenylhydrazido complexes, Mx(py)y[Ce(PhNNPh)4], M = Li, Na, and K, x = 4 (Li and Na) or 5 (K), and y = 4 (Li), 8 (Na), or 7 (K), were synthesized to probe how a secondary coordination sphere would modulate electronic structures at a cerium cation. The resulting electronic structures of the heterobimetallic cerium diphenylhydrazido complexes were found to be strongly dependent on the identity of the alkali metal cations. When M = Li+ or Na+, the cerium(III) starting material was oxidized with concomitant reduction of 1,2-diphenylhydrazine to aniline. Reduction of 1,2-diphenylhydrazine was not observedmore » when M = K+, and the complex remained in the cerium(III) oxidation state. Oxidation of the cerium(III) diphenylhydrazido complex to the Ce(IV) diphenylhydrazido one was achieved through a simple cation exchange reaction of the alkali metals. As a result, UV-Vis spectroscopy, FTIR spectroscopy, electrochemistry, magnetic susceptibility, and DFT studies were used to probe the oxidation state and the electronic changes that occurred at the metal centre.« less

  9. Extraction and coordination studies of a carbonyl-phosphine oxide scorpionate ligand with uranyl and lanthanide(III) nitrates: structural, spectroscopic and DFT characterization of the complexes.

    PubMed

    Matveeva, Anna G; Vologzhanina, Anna V; Goryunov, Evgenii I; Aysin, Rinat R; Pasechnik, Margarita P; Matveev, Sergey V; Godovikov, Ivan A; Safiulina, Alfiya M; Brel, Valery K

    2016-03-28

    Hybrid scorpionate ligand (OPPh2)2CHCH2C(O)Me (L) was synthesized and characterized by spectroscopic methods and X-ray diffraction. The selected coordination chemistry of L with UO2(NO3)2 and Ln(NO3)3 (Ln = La, Nd, Lu) has been evaluated. The isolated mono- and binuclear complexes, namely, [UO2(NO3)2L] (1), [{UO2(NO3)L}2(μ2-O2)]·EtOH (2), [La(NO3)3L2]·2.33MeCN (3), [Nd(NO3)3L2]·3MeCN (4), [Nd(NO3)2L2]+·(NO3)−·EtOH (5) and [Lu(NO3)3L2] (6) have been characterized by IR spectroscopy and elemental analysis. Single-crystal X-ray structures have been determined for complexes 1-5. Intramolecular intraligand π-stacking interactions between two phenyl fragments of the coordinated ligand(s) were observed in all complexes 1-5. The π-stacking interaction energy was estimated from Bader's AIM theory calculations performed at the DFT level. Solution properties have been examined using IR and multinuclear ((1)H, (13)C, and (31)P) NMR spectroscopy in CD3CN and CDCl3. Coordination modes of L vary with the coordination polyhedron of the metal and solvent nature showing many coordination modes: P(O),P(O), P(O),P(O),C(O), P(O),C(O), and P(O). Preliminary extraction studies of U(VI) and Ln(III) (Ln = La, Nd, Ho, Yb) from 3.75 M HNO3 into CHCl3 show that scorpionate L extracts f-block elements (especially uranium) better than its unmodified prototype (OPPh2)2CH2.

  10. In situ carbonyl extraction of Ni from gaseous diffusion cells

    SciTech Connect

    Visnapuu, A.; Hollenberg, G.W.; Bundy, R.D.

    1995-12-31

    This paper discusses the use of carbonyl processing technology for recovery of nickel from uranium isotope separation diffusion cells, and potential applications to recover nickel, iron, chromium, cobalt, and other carbonyl forming metals from nuclear waste while reducing the volume of the high level residue for more economic disposal. Nickel powder was carbonylated under static and dynamic conditions using only carbon monoxide to determine if the nickel powder would react rapidly enough to require no promoter. Nickel to Ni(CO){sub 4} conversion was realized in all cases and nickel metal was vapor deposited in the thermal decomposer, but the conversion rates in all cases the reaction were too slow for practical recovery. Addition of hydrogen sulfide gas as a promoter increased the conversion rate more than 500-fold over conversion with no promoter. Test summaries are provided in the paper; results indicate that promoter activated carbonylation is a viable approach for recovery of nickel from uranium isotope diffusion cells.

  11. Synthesis, characterization and thermal studies on metal complexes of new azo compounds derived from sulfa drugs

    NASA Astrophysics Data System (ADS)

    Mohamed, Gehad G.; Gad-Elkareem, Mohamed A. M.

    2007-12-01

    Four new azo ligands, L1 and HL2-4, of sulfa drugs have been prepared and characterized. [MX 2(L1)(H 2O) m]· nH 2O; [(MX 2) 2(HL2 or HL3)(H 2O) m]· nH 2O and [M 2X 3(L4)(H 2O)]· nH 2O; M = Co(II), Ni(II) and Cu(II) (X = Cl) and Zn(II) (X = AcO); m = 0-4 and n = 0-3, complexes were prepared. Elemental and thermal analyses (TGA and DTA), IR, solid reflectance spectra, magnetic moment and molar conductance measurements have accomplished characterization of the complexes. The IR data reveal that HL1 and HL2-3 ligands behave as a bidentate neutral ligands while HL4 ligand behaves as a bidentate monoionic ligand. They coordinated to the metal ions via the carbonyl O, enolic sulfonamide sbnd S(O)OH, pyrazole or thiazole N and azo N groups. The molar conductance data reveal that the chelates are non-electrolytes. From the solid reflectance spectra and magnetic moment data, the complexes were found to have octahedral, tetrahedral and square planar geometrical structures. The thermal behaviour of these chelates shows that the water molecules (hydrated and coordinated) and the anions are removed in a successive two steps followed immediately by decomposition of the ligand in the subsequent steps. The activation thermodynamic parameters, such as, E*, Δ H*, Δ S* and Δ G* are calculated from the TG curves applying Coats-Redfern method.

  12. Vibrational energy transfer dynamics in ruthenium polypyridine transition metal complexes.

    PubMed

    Fedoseeva, Marina; Delor, Milan; Parker, Simon C; Sazanovich, Igor V; Towrie, Michael; Parker, Anthony W; Weinstein, Julia A

    2015-01-21

    Understanding the dynamics of the initial stages of vibrational energy transfer in transition metal complexes is a challenging fundamental question which is also of crucial importance for many applications, such as improving the performance of solar devices or photocatalysis. The present study investigates vibrational energy transport in the ground and the electronic excited state of Ru(4,4'-(COOEt)2-2,2-bpy)2(NCS)2, a close relative of the efficient "N3" dye used in dye-sensitized solar cells. Using the emerging technique of ultrafast two-dimensional infrared spectroscopy, we show that, similarly to other transition-metal complexes, the central Ru heavy atom acts as a "bottleneck" making the energy transfer from small ligands with high energy vibrational stretching frequencies less favorable and thereby affecting the efficiency of vibrational energy flow in the complex. Comparison of the vibrational relaxation times in the electronic ground and excited state of Ru(4,4'-(COOEt)2-2,2-bpy)2(NCS)2 shows that it is dramatically faster in the latter. We propose to explain this observation by the intramolecular electrostatic interactions between the thiocyanate group and partially oxidised Ru metal center, which increase the degree of vibrational coupling between CN and Ru-N modes in the excited state thus reducing structural and thermodynamic barriers that slow down vibrational relaxation and energy transport in the electronic ground state. As a very similar behavior was earlier observed in another transition-metal complex, Re(4,4'-(COOEt)2-2,2'-bpy)(CO)3Cl, we suggest that this effect in vibrational energy dynamics might be common for transition-metal complexes with heavy central atoms.

  13. Infrared and microwave spectra of the acetylene-ammonia and carbonyl sulfide-ammonia complexes: a comparative study of a weak C-H···N hydrogen bond and an S···N bond.

    PubMed

    Liu, Xunchen; Xu, Yunjie

    2011-08-21

    We report a combined high resolution infrared and microwave spectroscopic investigation of the acetylene-ammonia and carbonyl sulfide-ammonia complexes using a pulsed slit-nozzle multipass absorption spectrometer based on a quantum cascade laser and a pulsed nozzle beam Fourier transform microwave spectrometer, respectively. The ro-vibrational transitions of the acetylene-ammonia complex have been measured at 6 μm in the vicinity of the ν(4) band of ammonia for the first time. The previously reported pure rotational transitions have been extended to higher J and K values with (14)N nuclear quadrupole hyperfine components detected and analyzed. The spectral analysis reveals that acetylene binds to ammonia through a C-H···N weak hydrogen bond to form a C(3v) symmetric top, consistent with the previous microwave [Fraser et al., J. Chem. Phys., 1984, 80, 1423] and infrared spectroscopic study at 3 μm [Hilpert et al., J. Chem. Phys., 1996, 105, 6183]. A parallel study has also been carried out for the carbonyl sulfide-ammonia complex whose pure rotational and ro-vibrational spectra at 6 μm have been detected and analyzed for the first time. The spectral and the subsequent structural analyses, in conjunction with the corresponding ab initio calculation, indicate that the OCS-NH(3) complex assumes C(3v) symmetry with S pointing to N of NH(3), in contrast to the T-shaped geometries obtained for the isoelectronic N(2)O-NH(3) and CO(2)-NH(3) complexes.

  14. Surface Complexation Modelling in Metal-Mineral-Bacteria Systems

    NASA Astrophysics Data System (ADS)

    Johnson, K. J.; Fein, J. B.

    2002-12-01

    The reactive surfaces of bacteria and minerals can determine the fate, transport, and bioavailability of aqueous heavy metal cations. Geochemical models are instrumental in accurately accounting for the partitioning of the metals between mineral surfaces and bacteria cell walls. Previous research has shown that surface complexation modelling (SCM) is accurate in two-component systems (metal:mineral and metal:bacteria); however, the ability of SCMs to account for metal distribution in mixed metal-mineral-bacteria systems has not been tested. In this study, we measure aqueous Cd distributions in water-bacteria-mineral systems, and compare these observations with predicted distributions based on a surface complexation modelling approach. We measured Cd adsorption in 2- and 3-component batch adsorption experiments. In the 2-component experiments, we measured the extent of adsorption of 10 ppm aqueous Cd onto either a bacterial or hydrous ferric oxide sorbent. The metal:bacteria experiments contained 1 g/L (wet wt.) of B. subtilis, and were conducted as a function of pH; the metal:mineral experiments were conducted as a function of both pH and HFO content. Two types of 3-component Cd adsorption experiments were also conducted in which both mineral powder and bacteria were present as sorbents: 1) one in which the HFO was physically but not chemically isolated from the system using sealed dialysis tubing, and 2) others where the HFO, Cd and B. subtilis were all in physical contact. The dialysis tubing approach enabled the direct determination of the concentration of Cd on each sorbing surface, after separation and acidification of each sorbent. The experiments indicate that both bacteria and mineral surfaces can dominate adsorption in the system, depending on pH and bacteria:mineral ratio. The stability constants, determined using the data from the 2-component systems, along with those for other surface and aqueous species in the systems, were used with FITEQL to

  15. Nonlinear d10-ML2 Transition-Metal Complexes

    PubMed Central

    Wolters, Lando P; Bickelhaupt, F Matthias

    2013-01-01

    We have investigated the molecular geometries of a series of dicoordinated d10-transition-metal complexes ML2 (M=Co−, Rh−, Ir−, Ni, Pd, Pt, Cu+, Ag+, Au+; L=NH3, PH3, CO) using relativistic density functional theory (DFT) at ZORA-BLYP/TZ2P. Not all complexes have the expected linear ligand–metal–ligand (L–M–L) angle: this angle varies from 180° to 128.6° as a function of the metal as well as the ligands. Our main objective is to present a detailed explanation why ML2 complexes can become bent. To this end, we have analyzed the bonding mechanism in ML2 as a function of the L–M–L angle using quantitative Kohn–Sham molecular orbital (MO) theory in combination with an energy decomposition analysis (EDA) scheme. The origin of bent L–M–L structures is π backdonation. In situations of strong π backdonation, smaller angles increase the overlap of the ligand’s acceptor orbital with a higher-energy donor orbital on the metal-ligand fragment, and therefore favor π backdonation, resulting in additional stabilization. The angle of the complexes thus depends on the balance between this additional stabilization and increased steric repulsion that occurs as the complexes are bent. PMID:24551547

  16. Polyimido sulfur(VI) phosphanyl ligand in metal complexation.

    PubMed

    Carl, Elena; Stalke, Dietmar

    2014-11-24

    Herein, new complexes containing the [Ph2PCH2S(NtBu)3](-) anion are presented, supplying three imido nitrogen atoms and a remote phosphorus atom as potential donor sites to main group and transition-metal cations. The lithiated complex [(tmeda)Li{(NtBu)3SCH2PPh2}] (1) is an excellent starting material in transmetalation reactions. Herein, the transition-metal complexes [M{(NtBu)3SCH2PPh2}2] (M=Mn (2), Ni (3), Zn (4)) were synthesized and structurally characterized. Their isotypical molecules show SN2 chelation and no employment of the adjacent phosphorus atom in coordination. The third pendent imido group is always twisted toward the vacant face of the tetrahedrally coordinated sulfur atom.

  17. Transition metal complexes of an isatinic quinolyl hydrazone

    PubMed Central

    2011-01-01

    Background The importance of the isatinic quinolyl hydrazones arises from incorporating the quinoline ring with the indole ring in the same compound. Quinoline ring has therapeutic and biological activities. On the other hand, isatin (1H-indole-2,3-dione) and its derivatives exhibit a wide range of biological activities. Also, the indole ring occurs in Jasmine flowers and Orange blossoms. Recently, the physiological and biological activities of quinolyl hydrazones arise from their tendency to form metal chelates with transition metal ions. In this context, we have reported to isolate, characterize and study the biological activity of some transition metal complexes of an isatinic quinolyl hydrazone; 3-[2-(4-methyl quinolin-2-yl)hydrazono] indolin-2-one. Results Mono- and binuclear as well as dimeric chelates were obtained from the reaction of a new isatinic quinolyl hydrazone with Fe(III), Co(II), Ni(II), Cu(II), VO(II) and Pd(II) ions. The ligand showed a variety of modes of bonding viz. (NNO)2-, (NO)- and (NO) per each metal ion supporting its ambidentate and flexidentate characters. The mode of bonding and basicity of the ligand depend mainly on the type of the metal cation and its counter anion. All the obtained Pd(II)- complexes have the preferable square planar geometry (D4h- symmetry) and depend mainly on the mole ratio (M:L). Conclusion The effect of the type of the metal ion for the same anion (Cl-) is obvious from either structural diversity of the isolated complexes (Oh, Td and D4h) or the various modes of bonding. The isatinic hydrazone uses its lactim form in all complexes (Cl-) except complex 5 (SO42-) in which it uses its lactam form. The obtained Pd(II)- complexes (dimeric, mono- and binuclear) are affected by the mole ratio (M:L) and have the square planar (D4h) geometry. Also, the antimicrobial activity is highly influenced by the nature of the metal ion and the order for S. aureus bacteria is as follows: Nickel(II) > Vanadyl(II) > Cobalt

  18. Surface decorated platinum carbonyl clusters

    NASA Astrophysics Data System (ADS)

    Ciabatti, Iacopo; Femoni, Cristina; Iapalucci, Maria Carmela; Longoni, Giuliano; Zacchini, Stefano; Zarra, Salvatore

    2012-06-01

    Four molecular Pt-carbonyl clusters decorated by Cd-Br fragments, i.e., [Pt13(CO)12{Cd5(μ-Br)5Br2(dmf)3}2]2- (1), [Pt19(CO)17{Cd5(μ-Br)5Br3(Me2CO)2}{Cd5(μ-Br)5Br(Me2CO)4}]2- (2), [H2Pt26(CO)20(CdBr)12]8- (3) and [H4Pt26(CO)20(CdBr)12(PtBr)x]6- (4) (x = 0-2), have been obtained from the reactions between [Pt3n(CO)6n]2- (n = 2-6) and CdBr2.H2O in dmf at 120 °C. The structures of these molecular clusters with diameters of 1.5-2 nm have been determined by X-ray crystallography. Both 1 and 2 are composed of icosahedral or bis-icosahedral Pt-CO cores decorated on the surface by Cd-Br motifs, whereas 3 and 4 display a cubic close packed Pt26Cd12 metal frame decorated by CO and Br ligands. An oversimplified and unifying approach to interpret the electron count of these surface decorated platinum carbonyl clusters is suggested, and extended to other low-valent organometallic clusters and Au-thiolate nanoclusters.Four molecular Pt-carbonyl clusters decorated by Cd-Br fragments, i.e., [Pt13(CO)12{Cd5(μ-Br)5Br2(dmf)3}2]2- (1), [Pt19(CO)17{Cd5(μ-Br)5Br3(Me2CO)2}{Cd5(μ-Br)5Br(Me2CO)4}]2- (2), [H2Pt26(CO)20(CdBr)12]8- (3) and [H4Pt26(CO)20(CdBr)12(PtBr)x]6- (4) (x = 0-2), have been obtained from the reactions between [Pt3n(CO)6n]2- (n = 2-6) and CdBr2.H2O in dmf at 120 °C. The structures of these molecular clusters with diameters of 1.5-2 nm have been determined by X-ray crystallography. Both 1 and 2 are composed of icosahedral or bis-icosahedral Pt-CO cores decorated on the surface by Cd-Br motifs, whereas 3 and 4 display a cubic close packed Pt26Cd12 metal frame decorated by CO and Br ligands. An oversimplified and unifying approach to interpret the electron count of these surface decorated platinum carbonyl clusters is suggested, and extended to other low-valent organometallic clusters and Au-thiolate nanoclusters. CCDC 867747 and 867748. For crystallographic data in CIF or other electronic format see DOI: 10.1039/c2nr30400g

  19. Marine metabolites: metal binding and metal complexes of azole-based cyclic peptides of marine origin.

    PubMed

    Bertram, Anna; Pattenden, Gerald

    2007-02-01

    Azole-based cyclic peptides found in ascidians ("sea squirts") of the genus Lissoclinum have a high propensity to chelate metal ions. This Highlight summarises the current evidence for marine cyclic peptide-metal congruence, and the structural and stereochemical features in cyclic peptides which seem necessary to facilitate metal complexation. The biological relevance of the metal ions in these associations, including their possible role in the assembly of cyclic peptides in the marine milieu, is also briefly considered. Finally, the synthesis of natural, and some novel non-natural, azole-based cyclic peptides from the cyclooligomerisation and assembly of azole-based amino acids, including in the presence of metal ions, is presented.

  20. Electron transfer and catalysis with high-valent metal-oxo complexes.

    PubMed

    Fukuzumi, Shunichi

    2015-04-21

    High-valent metal-oxo complexes are produced by reductive activation of dioxygen via reduction of metal complexes with reductants and dioxygen. Photoinduced electron transfer from substrates to metal complexes with dioxygen also leads to the generation of high-valent metal-oxo complexes that can oxygenate substrates. In such a case metal complexes act as a photocatalyst to oxygenate substrates with dioxygen. High-valent metal-oxo complexes are also produced by proton-coupled electron-transfer oxidation of metal complexes by one-electron oxidants with water, oxygenating substrates to regenerate metal complexes. In such a case metal complexes act as a catalyst for electron-transfer oxygenation of substrates by one-electron oxidants with water that acts as an oxygen source. The one-electron oxidants which can oxidize metal complexes can be replaced by much weaker oxidants by a combination of redox photocatalysts and metal complexes. Thus, photocatalytic oxygenation of substrates proceeds via photoinduced electron transfer from a photocatalyst to reductants followed by proton-coupled electron transfer oxidation of metal complexes with the oxidized photocatalyst to produce high-valent metal-oxo complexes that oxygenate substrates. Thermal and photoinduced electron-transfer catalytic reactions of high-valent metal-oxo complexes for oxygenation of substrates using water or dioxygen as an oxygen source are summarized in this perspective.

  1. Transition-metal complexes containing parent phosphine or phosphinyl ligands and their use as precursors for phosphide nanoparticles.

    PubMed

    Bauer, Susanne; Hunger, Cornelia; Bodensteiner, Michael; Ojo, Wilfried-Solo; Cros-Gagneux, Arnaud; Chaudret, Bruno; Nayral, Céline; Delpech, Fabien; Scheer, Manfred

    2014-11-03

    P-H functional transition-metal complexes were synthesized without using hazardous PH3 gas in good yields by photolysis of the transition-metal carbonyl complexes M(CO)(6-x) (M = Cr, W, Fe; x = 0, 1) in tetrahydrofuran followed by reaction with P2(SiMe3)4 and subsequent methanolysis to give the bridging complexes [(CO)(x)M(μ-PH2)]2 (M = Fe, x = 3 (1), M = Cr, x = 4 (2a), M = W, x = 4 (2b)). The photolysis of [(CO)4M(μ-PH2)]2 (M = Cr (2a), M = W (2b)) with P(SiMe3)3 was applied followed by methanolysis to synthesize the PH2 bridging transition-metal binuclear complexes with terminal PH3 groups. The products [(CO)4M(μ-PH2)2M(CO)3(PH3)] (M = Cr (3a), M = W (3b)) and [(CO)4W(μ-PH2)2W(CO)2(PH3)2] (4b) were isolated in moderate yield. Another synthetic approach to this type of compounds is the direct photolysis of the complexes [(CO)3M(PH3)3] (M = Cr (5a), M = W (5b)). The products were comprehensively characterized by (31)P NMR and IR spectroscopy as well as by X-ray structural analysis. Additionally, the relevancy of 2a as single source precursor for the synthesis of stoichiometry-controlled CrP nanoparticles has been demonstrated.

  2. Survey of metal finishing capabilities in the Nuclear Weapons Complex

    SciTech Connect

    Johnson, H.R.; Stoltz, R.E.

    1990-12-01

    This report presents the results of a survey of the metal finishing capabilities of the following design and production agencies in the Nuclear Weapon Complex: Allied Signal Aerospace Co. (AS), General Electric Neutron Device Division (GEND), Los Alamos National Laboratory (LANL), Lawrence Livermore National Laboratory (LLNL), EG G Mound Applied Technology (MD), EG G Rocky Flats Plant (RF), Sandia National Laboratories, Albuquerque (SNL, A), Sandia National Laboratories, Livermore (SNL, L) and Martin Marietta Energy Systems, Inc. (Y-12). It defines the current status of electroplating and its allied processes at each of these agencies, the methods and procedures for handling waste, and the major environmental, safety, and health issues confronting metal finishing personnel.

  3. Ternary metal complexes of guaifenesin drug: Synthesis, spectroscopic characterization and in vitro anticancer activity of the metal complexes.

    PubMed

    Mahmoud, W H; Mahmoud, N F; Mohamed, G G; El-Sonbati, A Z; El-Bindary, A A

    2015-01-01

    The coordination behavior of a series of transition metal ions named Cr(III), Fe(III), Mn(II), Co(II), Ni(II), Cu(II), Zn(II) and Cd(II) with a mono negative tridentate guaifenesin ligand (GFS) (OOO donation sites) and 1,10-phenanthroline (Phen) is reported. The metal complexes are characterized based on elemental analyses, IR, (1)H NMR, solid reflectance, magnetic moment, molar conductance, UV-vis spectral studies, mass spectroscopy, ESR, XRD and thermal analysis (TG and DTG). The ternary metal complexes were found to have the formulae of [M(GFS)(Phen)Cl]Cl·nH2O (M=Cr(III) (n=1) and Fe(III) (n=0)), [M(GFS)(Phen)Cl]·nH2O (M=Mn(II) (n=0), Zn(II) (n=0) and Cu(II) (n=3)) and [M(GFS)(Phen)(H2O)]Cl·nH2O (M=Co(II) (n=0), Ni(II) (n=0) and Cd(II) (n=4)). All the chelates are found to have octahedral geometrical structures. The ligand and its ternary chelates are subjected to thermal analyses (TG and DTG). The GFS ligand, in comparison to its ternary metal complexes also was screened for their antibacterial activity on gram positive bacteria (Bacillus subtilis and Staphylococcus aureus), gram negative bacteria (Escherichia coli and Neisseria gonorrhoeae) and for in vitro antifungal activity against (Candida albicans). The activity data show that the metal complexes have antibacterial and antifungal activity more than the parent GFS ligand. The complexes were also screened for its in vitro anticancer activity against the Breast cell line (MFC7) and the results obtained show that they exhibit a considerable anticancer activity. Copyright © 2015 Elsevier B.V. All rights reserved.

  4. Synthesis, spectroscopic characterization, electrochemical behaviour, reactivity and antibacterial activity of some transition metal complexes with 2-( N-salicylideneamino)-3-carboxyethyl-4,5-dimethylthiophene

    NASA Astrophysics Data System (ADS)

    Daniel, Varughese P.; Murukan, B.; Kumari, B. Sindhu; Mohanan, K.

    2008-07-01

    Mn(II), Fe(II), Co(II), Ni(II), Cu(II) and Zn(II) complexes with a potentially tridentate Schiff base, formed by condensation of 2-amino-3-carboxyethyl-4,5-dimethylthiophene with salicylaldehyde were synthesized and characterized on the basis of elemental analyses, molar conductance values, magnetic susceptibility measurements, UV-vis, IR, EPR and NMR spectral data, wherever possible and applicable. Spectral studies reveal that the free ligand exists in a bifunctionally hydrogen bonded manner and coordinates to the metal ion in a tridentate fashion through the deprotonated phenolate oxygen, azomethine nitrogen and ester carbonyl group. On the basis of electronic spectral data and magnetic susceptibility measurements, suitable geometry has been proposed for each complex. The EPR spectral data of the Cu(II) complex showed that the metal-ligand bonds have considerable covalent character. The Ni(II) complex has undergone facile transesterification reaction when refluxed in methanol for a lengthy period. X-ray diffraction studies of Cu(II) complex showed that the complex has an orthorhombic crystal lattice. In view of the biological activity of thiophene derivatives, the ligand and the complexes were subjected to antibacterial screening. It has been observed that the antibacterial activity of the ligand increased on chelation with metal ion.

  5. Linkage isomerism of carbonyl coordination complexes formed upon CO adsorption on the zeolite Li-ZSM-5: variable-temperature FTIR studies

    NASA Astrophysics Data System (ADS)

    Otero Areán, C.; Rodríguez Delgado, M.; Manoilova, O. V.; Turnes Palomino, G.; Tsyganenko, A. A.; Garrone, E.

    2002-08-01

    Carbon monoxide adsorbed at a low-temperature on the zeolite Li-ZSM-5 forms Li +⋯CO and Li +⋯(CO) 2 species characterized by C-O stretching bands at 2195 and 2187 cm-1, respectively. These C-bonded carbonyls are in a temperature-dependent equilibrium with Li +⋯OC and CO⋯Li +⋯CO species having O-bonded CO. By means of variable-temperature FTIR spectroscopy, the enthalpy change involved in the corresponding isomerization process was found to be ΔH°=7.8 kJ mol-1 for the monocarbonyl and ΔH°=5.1 kJ mol-1 for the dicarbonyl. Therefore, although C-bonded species were always found to show a higher cation-CO interaction energy than O-bonded species, the difference is smaller in the case of dicarbonyls.

  6. Spectral characterization, optical band gap calculations and DNA binding of some binuclear Schiff-base metal complexes derived from 2-amino-ethanoic acid and acetylacetone

    NASA Astrophysics Data System (ADS)

    Hussien, Mostafa A.; Nawar, Nagwa; Radwan, Fatima M.; Hosny, Nasser Mohammed

    2015-01-01

    Bi-nuclear metal complexes derived from the reaction of Cu(II), Co(II), Ni(II) and Zn(II) acetates with the Schiff-base ligand (H2L) resulted from the condensation of 2-amino-ethanoic acid (glycine) and acetylacetone have been synthesized and characterized by elemental analyses, Raman spectra, FT-IR, ES-MS, UV-Vis., 1H NMR, ESR, thermal analyses (TG, DTG and DTA) and magnetic measurements. The results showed that, the Schiff base ligand can bind two metal ions in the same time. It coordinates to the first metal ion as mono-negative bi-dentate through azomethine nitrogen and enolic carbonyl after deprotonation. At the same time, it binds to the second metal ion via carboxylate oxygen after deprotonation. The thermodynamic parameters E∗, ΔH∗, ΔG∗ and ΔS∗ have been calculated by Coats-Redfern (CR) and Horowitz-Metzger (HM) methods. The optical band gaps of the isolated complexes have been calculated from absorption spectra and the results indicated semi-conducting nature of the investigated complexes. The interactions between the copper (II) complex and calf thymus DNA (CT-DNA) have been studied by UV spectra. The results confirm that the Cu(II) complex binds to CT-DNA.

  7. Green synthesis of multi metal- citrate complexes and their characterization

    NASA Astrophysics Data System (ADS)

    Raju, Usha; Warkar, Sudhir G.; Kumar, Anil

    2017-04-01

    Four new multi metal-citrate complexes have been synthesized through green synthetic pathways. Their synthesis by hydrothermal route in the present research is decorated with features such as, a simple one pot synthesis, cost effectiveness, easy to scale up for commercial production, efficient synthesis conditions like mild temperature and shorter duration which further rules out the possibility of forming byproducts which may cause damage to the environment and being environmental benign as it eliminates the use and recovery of harmful organic solvents such as N, N- dimethyl formamide and N, N- diethyl formamide, used by the researchers in the past during the synthesis of similar metal- organic framework complexes. All four complexes are well defined crystalline materials with polynuclear multi metal-citrate framework having cubic crystal structure as indicated by their Powder X-ray Diffraction patterns. These complexes have been characterized by Fourier Transform Infrared Spectroscopy, Scanning Electron Microscopy, Energy Dispersive X-ray Spectroscopy, Thermogravimetric analysis and Powder XRD techniques.

  8. Simple charge-transfer model for metallic complexes.

    PubMed

    Ramírez-Ramírez, José-Zeferino; Vargas, Rubicelia; Garza, Jorge; Gázquez, José L

    2010-08-05

    In the chemistry of metallic complexes, two important concepts have been used to rationalize the recognition and selectivity of a host by a guest: preorganization and complementarity. Both of these concepts stem from geometrical features. Less explored in the literature has been the interactional complementarity, where mainly the electronic factors in the intermolecular forces are involved. Because the charge transfer between a species rich in electrons (ligand) and another deficient in them (cation) is one of the main intermolecular factors that control the binding energies in metallic complexes, for such systems, we propose a simple model based on density functional theory. We define an interactional energy in which the geometrical energy changes are subtracted from the binding energies and just the electronic factors are taken into account. The model is tested for the complexation between bidentate and cyclic ligands and Ca, Pb, and Hg metal dications. The charge-transfer energy described by our model fits nicely with the interactional energy. Thus, when the geometrical changes do not contribute in a significant way to the complexation energy, the interactional energy is dominated by charge-transfer effects.

  9. Metal Complexes for DNA-Mediated Charge Transport

    PubMed Central

    Barton, Jacqueline K.; Olmon, Eric D.; Sontz, Pamela A.

    2010-01-01

    In all organisms, oxidation threatens the integrity of the genome. DNA-mediated charge transport (CT) may play an important role in the generation and repair of this oxidative damage. In studies involving long-range CT from intercalating Ru and Rh complexes to 5′-GG-3′ sites, we have examined the efficiency of CT as a function of distance, temperature, and the electronic coupling of metal oxidants bound to the base stack. Most striking is the shallow distance dependence and the sensitivity of DNA CT to how the metal complexes are stacked in the helix. Experiments with cyclopropylamine-modified bases have revealed that charge occupation occurs at all sites along the bridge. Using Ir complexes, we have seen that the process of DNA-mediated reduction is very similar to that of DNA-mediated oxidation. Studies involving metalloproteins have, furthermore, shown that their redox activity is DNA-dependent and can be DNA-mediated. Long range DNA-mediated CT can facilitate the oxidation of DNA-bound base excision repair proteins to initiate a redox-active search for DNA lesions. DNA CT can also activate the transcription factor SoxR, triggering a cellular response to oxidative stress. Indeed, these studies show that within the cell, redox-active proteins may utilize the same chemistry as that of synthetic metal complexes in vitro, and these proteins may harness DNA-mediated CT to reduce damage to the genome and regulate cellular processes. PMID:21643528

  10. Selective transformations of cyclopentadienyl ligands of transition-metal and rare-earth metal complexes.

    PubMed

    Liu, Ruiting; Zhou, Xigeng

    2013-04-21

    Cyclopentadienyl and substituted cyclopentadienyl ligands are observed in a wide range of organometallic complexes. In addition to serving as ancillary ligands, these ligands have come into their own as intermediates in organometallic reactions, and shown many unique reaction modes involving ring C-H, C-C and C=C bond cleavages. This feature article summarizes the progressive development of cyclopentadienyl-based reactions of metallocene complexes of transition metals and rare-earth metals, with the aim of further developing the fundamental modes of reactivity of such systems together with their synthetic applications.

  11. Photoinduced energy transfer in transition metal complex oligomers

    SciTech Connect

    1997-04-01

    The work we have done over the past three years has been directed toward the preparation, characterization and photophysical examination of mono- and bimetallic diimine complexes. The work is part of a broader project directed toward the development of stable, efficient, light harvesting arrays of transition metal complex chromophores. One focus has been the synthesis of rigid bis-bidentate and bis-tridentate bridging ligands. We have managed to make the ligand bphb in multigram quantities from inexpensive starting materials. The synthetic approach used has allowed us prepare a variety of other ligands which may have unique applications (vide infra). We have prepared, characterized and examined the photophysical behavior of Ru(II) and Re(I) complexes of the ligands. Energy donor/acceptor complexes of bphb have been prepared which exhibit nearly activationless energy transfer. Complexes of Ru(II) and Re(I) have also been prepared with other polyunsaturated ligands in which two different long lived ( > 50 ns) excited states exist; results of luminescence and transient absorbance measurements suggest the two states are metal-to-ligand charge transfer and ligand localized {pi}{r_arrow}{pi}* triplets. Finally, we have developed methods to prepare polymetallic complexes which are covalently bound to various surfaces. The long term objective of this work is to make light harvesting arrays for the sensitization of large band gap semiconductors. Details of this work are provided in the body of the report.

  12. Photoinduced energy transfer in transition metal complex oligomers

    SciTech Connect

    1997-06-01

    The work done over the past three years has been directed toward the preparation, characterization and photophysical examination of mono- and bimetallic diimine complexes. The work is part of a broader project directed toward the development of stable, efficient, light harvesting arrays of transition metal complex chromophores. One focus has been the synthesis of rigid bis-bidentate and bis-tridentate bridging ligands. The authors have managed to make the ligand bphb in multigram quantities from inexpensive starting materials. The synthetic approach used has allowed them to prepare a variety of other ligands which may have unique applications (vide infra). They have prepared, characterized and examined the photophysical behavior of Ru(II) and Re(I) complexes of the ligands. Energy donor/acceptor complexes of bphb have been prepared which exhibit nearly activationless energy transfer. Complexes of Ru(II) and Re(I) have also been prepared with other polyunsaturated ligands in which two different long lived (> 50 ns) excited states exist; results of luminescence and transient absorbance measurements suggest the two states are metal-to-ligand charge transfer and ligand localized {pi}{r_arrow}{pi}* triplets. Finally, the authors have developed methods to prepare polymetallic complexes which are covalently bound to various surfaces. The long term objective of this work is to make light harvesting arrays for the sensitization of large band gap semiconductors. Details of this work are provided in the body of the report.

  13. Interplay of metal-allyl and metal-metal bonding in dimolybdenum allyl complexes

    SciTech Connect

    John, Kevin D; Martin, Richard L; Obrey, Steven J; Scott, Brian L

    2008-01-01

    Addition of PMe{sub 3} to Mo{sub 2}(allyl){sub 4} afforded Mo{sub 2}(allyl){sub 4}(PMe{sub 3}){sub 2}, in which two of the allyl groups adopt an unprecedented {mu}{sub 2{sup -}}{eta}{sup 1}, {eta}{sup 3} bonding mode; theoretical studies elucidate the role sof the {sigma}- and {pi}-donor ligands in the interplay of metal-allyl and metal-metal bonding.

  14. Electric relaxation processes in chemodynamics of aqueous metal complexes: from simple ligands to soft nanoparticulate complexants.

    PubMed

    van Leeuwen, Herman P; Buffle, Jacques; Town, Raewyn M

    2012-01-10

    The chemodynamics of metal complexes with nanoparticulate complexants can differ significantly from that for simple ligands. The spatial confinement of charged sites and binding sites to the nanoparticulate body impacts on the time scales of various steps in the overall complex formation process. The greater the charge carried by the nanoparticle, the longer it takes to set up the counterion distribution equilibrium with the medium. A z+ metal ion (z > 1) in a 1:1 background electrolyte will accumulate in the counterionic atmosphere around negatively charged simple ions, as well as within/around the body of a soft nanoparticle with negative structural charge. The rate of accumulation is often governed by diffusion and proceeds until Boltzmann partition equilibrium between the charged entity and the ions in the medium is attained. The electrostatic accumulation proceeds simultaneously with outer-sphere and inner-sphere complex formation. The rate of the eventual inner-sphere complex formation is generally controlled by the rate constant of dehydration of the metal ion, k(w). For common transition metal ions with moderate to fast dehydration rates, e.g., Cu(2+), Pb(2+), and Cd(2+), it is shown that the ionic equilibration with the medium may be the slower step and thus rate-limiting in their overall complexation with nanoparticles.

  15. Solution structure of a metal-binding site in the major groove of RNA complexed with cobalt (III) hexammine.

    PubMed

    Kieft, J S; Tinoco, I

    1997-05-15

    Solvated metal ions are critical for the proper folding and function of RNA. Despite the importance of these ions, the details of specific metal ion-RNA interactions are poorly understood. The crystal structure of a group I intron ribozyme domain characterized several metal-binding sites in the RNA with osmium (III) hexammine bound in the major groove. A corresponding method for locating and characterizing metal-binding sites of RNA in solution is of obvious interest. NMR should be ideal for localizing metal hexammine ions bound to the RNA because of the large concentration of protons around the metal center. We have solved the solution structure of the P5b stem loop from a group I intron ribozyme bound to a cobalt (III) hexammine ion. The location of the ion is precisely determined by intermolecular nuclear Overhausser effect cross-peaks between the cobalt (III) hexammine protons and both exchangeable and non-exchangeable RNA protons in the major groove. The binding site consists of tandem G-U base pairs in a sequence of four consecutive G residues ending in a GAAA tetraloop, as originally identified in the crystal structure. The edges of the bases in the major groove present an electrostatically negative face and a variety of hydrogen-bond acceptors for the cobalt (III) hexammine ion. The metal ion ligand is bound near the guanosine nucleotides of the adjacent G-U base pairs, where it makes hydrogen bonds with the N7 and carbonyl groups of both guanines. The carbonyl groups of the uracil residues add to the negative surface of the binding pocket, but do not form hydrogen bonds with the hexammine. Additional hydrogen bonds form with other guanine residues of the GGGG sequence. The structure of the binding site does not change significantly on binding the cobalt (III) hexammine. The structure of the complex in solution is very similar to the structure in the crystal. The structure presents a picture of how tandem G-U base pairs bind and position metal ions within

  16. Structural rearrangements induced by acid-base reactions in metal carbonyl clusters: the case of [H(3-n)Co15Pd9C3(CO)38]n- (n = 0-3).

    PubMed

    Ciabatti, Iacopo; Femoni, Cristina; Gaboardi, Mattia; Iapalucci, Maria Carmela; Longoni, Giuliano; Pontiroli, Daniele; Riccò, Mauro; Zacchini, Stefano

    2014-03-21

    The new bimetallic [HCo15Pd9C3(CO)38](2-) tri-carbide carbonyl cluster has been obtained from the reaction of [H2Co20Pd16C4(CO)48](4-) with an excess of acid in CH2Cl2 solution. The mono-hydride di-anion can be reversibly protonated and deprotonated by means of acid-base reactions leading to closely related [H(3-n)Co15Pd9C3(CO)38](n-) (n = 0-3) clusters. The crystal structures of the three anionic and the neutral clusters have been determined as their H3Co15Pd9C3(CO)38·2thf, [NEt4][H2Co15Pd9C3(CO)38]·0.5C6H14, [NMe3(CH2Ph)]2[HCo15Pd9C3(CO)38]·C6H14 and [NEt4]3[Co15Pd9C3(CO)38]·thf salts. They are composed of a Pd9(μ3-CO)2 core stabilised by three Co5C(CO)12 organometallic fragments. The poly-hydride nature of these clusters has been indirectly inferred via chemical, electrochemical and magnetic measurements. Besides, cyclic voltammetry shows that the [H(3-n)Co15Pd9C3(CO)38](n-) (n = 1-3) anions are multivalent, since they undergo two or three reversible oxidations. SQUID measurements of [HCo15Pd9C3(CO)38](2-) indicate that this even electron cluster is paramagnetic with two unpaired electrons, giving further support to its hydride nature. Finally, structural studies show that the Pd9 core of [H(3-n)Co15Pd9C3(CO)38](n-) (n = 0,1) is a tri-capped octahedron, which becomes a tri-capped trigonal prism in the more charged [H(3-n)Co15Pd9C3(CO)38](n-) (n = 2,3) anions. Such a significant structural rearrangement of the metal core of a large carbonyl cluster upon protonation-deprotonation reactions is unprecedented in cluster chemistry, and suggests that interstitial hydrides may have relevant stereochemical effects even in large carbonyl clusters.

  17. Bis(hydroxylaminato)-mono(pentamethylcyclopentadienyl) rare-earth metal complexes.

    PubMed

    Venugopal, Ajay; Pape, Tania; Willner, Alexander; Mitzel, Norbert W

    2009-08-07

    Salt metathesis reactions involving the anhydrous rare-earth metal trichlorides MCl(3) (M = Y, Ho, Er and Lu) and the N,N-diethylhydroxylaminato potassium salt, KONEt(2) (1), and KC(5)Me(5) result in formation of rare-earth metal hydroxylaminato complexes of the type [(C(5)Me(5))M(mu-eta(1):eta(2)-ONEt(2))(eta(2)-ONEt(2))](2) (M = Y (2a), Ho (2b), Er (2c) and Lu (2d)). Compound 1 was characterised by elemental analysis, compounds 2a and 2d by NMR spectroscopy and compounds 2a-d by elemental analyses, mass-spectrometry and single crystal X-ray diffraction. Compounds 2a-d are isostructural in the solid state. Effective saturation of the coordination sphere of the rare-earth metal atoms by the hydroxylaminato groups is achieved by the formation of three-membered MON rings.

  18. Inhomogeneous complexation of trace metals in water with organic nano-complexants

    NASA Astrophysics Data System (ADS)

    Dolgin, Bella; Bulatov, Valery; Hadar-Abuhatzira, Hodayah; Japarov, Julia; Schechter, Israel

    2011-12-01

    The complexation of heavy metals, such as Cd 2+ and Ni 2+, with organic complexants such as 1-(2-pyridylazo)-2-naphthol (PAN) and 1-(2-thiazolylazo)-2-naphthol (TAN) in water has been investigated. Under such conditions, both the reagents and the products form nano-particulates. These materials are important because their spectrum changes upon exposure to heavy metals and they may be used for design of new optical detectors. The kinetic schemes so far suggested for these complexation reactions are not valid for such experimental conditions, since they assume homogeneous behavior. We provide evidences to the inhomogeneous nature of these reactions. The complexation has been studied using TEM imaging, zeta-potentiometry, time-dependent particulate size analysis and time-dependent spectroscopy. Many of the experimental results are explained in terms of the nature of the nano-particulates of these two complexants. Several processes were identified, including crystal growing of the complexant, its reaction with metal ions in solution and on the surface area, chemical erosion of complexant crystallites and their decomposition, re-crystallization of the formed complexes and long term aggregation of both the complexant and the resulted complex. It was found that the needle-like nano-structures on the surface of the TAN particulates governs its reaction and particulate behavior. The known optimal complexation conditions, such as pH, and delay time are now understood in terms of the zeta-potential minima of the suspensions and in terms of the kinetic parameters. Also the interferences of some ions in the Ni-TAN complexation are now quantified and the kinetic data indicate the best delay time when the interfering effects are minimal.

  19. Polynuclear transition metal complexes with thiocarbohydrazide and dithiocarbamates

    NASA Astrophysics Data System (ADS)

    Siddiqi, K. S.; Khan, Sadaf; Nami, Shahab A. A.; El-ajaily, M. M.

    2007-07-01

    Sn(tch) 2{MCl 2} 2 was prepared from the precursor Sn(tch) 2 and MCl 2. It was subsequently allowed to react with diethyldithiocarbamate which yielded the trinuclear complexes of the type Sn(tch) 2{M 2(dtc) 4}, where tch = thiocarbohydrazide, M = Mn(II), Fe(II), Co(II), Ni(II), Cu(II) and dtc = diethyldithiocarbamate. They were characterized on the basis of microanalytical, thermal (TGA/DSC), spectral (IR, UV-vis, EPR, 1H NMR) studies, conductivity measurement and magnetic moment data. On the basis of spectral data a tetrahedral geometry has been proposed for the halide complexes, Sn(tch) 2{MCl 2} 2 except for Cu(II) which exhibits a square planar coordination although the transition metal ion in Sn(tch) 2{M 2(dtc) 4} achieves an octahedral geometry where the dithiocarbamato moiety acts as a symmetrical bidentate ligand. The bidentate nature has been established by the appearance of a sharp single ν(C-S) around 1000 cm -1. A downfield shift observed in NH a and NH b protons on moving from Sn(tch) 2 to Sn(tch) 2{MCl 2} 2 is due to the drift of electrons toward metal atoms. A two-step pyrolysis has been observed in the Sn(tch) 2{MCl 2} 2 complexes while their dithiocarbamato derivatives exhibit a three-stage degradation pattern. Finally, the in vitro antibacterial activity of Sn(tch) 2{M 2(dtc) 4} and the mononuclear Sn(tch) 2 has been carried out on bacterial strains Escherichia coli and Salmonella typhi. The compounds were found to be active against the test organisms. The activity of the complexes is enhanced with increasing concentration. The maximum activity in both the strains was achieved by cobalt(II) dithiocarbamate complex. Minimum activity was found for Sn(tch) 2 which generally increases with the introduction of transition metal ion in the complex.

  20. Blue metal complex pigments involved in blue flower color

    PubMed Central

    Takeda, Kosaku

    2006-01-01

    The blue pigment of cornflower, protocyanin, has been investigated for a long time, but its precise structure was not entirely explained until recently. The molecular structure of the pigment was recently shown to be a metal complex of six molecules each of anthocyanin and flavone glycoside, with one ferric iron, one magnesium and two calcium ions by X-ray crystallographic analysis. The studies provided the answer to the question posed in the early part of the last century, “why is the cornflower blue and rose red when both flowers contain the same anthocyanin?” This work was achieved on the basis of the results of long years of the studies made by many researchers. In this review, the author focuses on the investigations of the blue metal complex pigments involved in the bluing of flowers, commelinin from Commelina commusis, protocyanin from Centaurea cyanus, protodelphin from Salvia patens and hydrangea blue pigment. PMID:25792777

  1. Blue metal complex pigments involved in blue flower color.

    PubMed

    Takeda, Kosaku

    2006-05-01

    The blue pigment of cornflower, protocyanin, has been investigated for a long time, but its precise structure was not entirely explained until recently. The molecular structure of the pigment was recently shown to be a metal complex of six molecules each of anthocyanin and flavone glycoside, with one ferric iron, one magnesium and two calcium ions by X-ray crystallographic analysis. The studies provided the answer to the question posed in the early part of the last century, "why is the cornflower blue and rose red when both flowers contain the same anthocyanin?" This work was achieved on the basis of the results of long years of the studies made by many researchers. In this review, the author focuses on the investigations of the blue metal complex pigments involved in the bluing of flowers, commelinin from Commelina commusis, protocyanin from Centaurea cyanus, protodelphin from Salvia patens and hydrangea blue pigment.

  2. Dynamic inclusion complexes of metal nanoparticles inside nanocups.

    PubMed

    Alarcón-Correa, Mariana; Lee, Tung-Chun; Fischer, Peer

    2015-06-01

    Host-guest inclusion complexes are abundant in molecular systems and of fundamental importance in living organisms. Realizing a colloidal analogue of a molecular dynamic inclusion complex is challenging because inorganic nanoparticles (NPs) with a well-defined cavity and portal are difficult to synthesize in high yield and with good structural fidelity. Herein, a generic strategy towards the fabrication of dynamic 1:1 inclusion complexes of metal nanoparticles inside oxide nanocups with high yield (>70%) and regiospecificity (>90%) by means of a reactive double Janus nanoparticle intermediate is reported. Experimental evidence confirms that the inclusion complexes are formed by a kinetically controlled mechanism involving a delicate interplay between bipolar galvanic corrosion and alloying-dealloying oxidation. Release of the NP guest from the nanocups can be efficiently triggered by an external stimulus.

  3. Tetravalent metal complexation by Keggin and lacunary phosphomolybdate anions.

    PubMed

    Copping, Roy; Jonasson, Leif; Gaunt, Andrew J; Drennan, Dennis; Collison, David; Helliwell, Madeleine; Pirttijarvi, Ross J; Jones, Chris J; Huguet, Anne; Apperley, David C; Kaltsoyannis, Nikolas; May, Iain

    2008-07-07

    We report the synthesis, spectroscopic and structural characterization, and computational analysis of a series of phosphomolybdate complexes with tetravalent metal cations. The reaction between Ce (IV) and Th (IV) with phosphomolybdate at the optimum pH for the stabilization of the lacunary heteropolyoxometalate anion, [PMo 11O 39] (7-), results in the formation of compounds containing the anions [Ce(PMo 11O 39) 2] (10-) and [Th(PMo 11O 39) 2] (10-), respectively. Single crystal X-ray diffraction analysis was performed on salts of both species, Cs 10[Ce(PMo 11O 39) 2].20H 2O and (NH 4) 10[Th(PMo 11O 39) 2].22H 2O. In both anionic complexes the f-block metal cation is coordinated to the four unsaturated terminal lacunary site oxygens of each [PMo 11O 39] (7-) anion, yielding 8 coordinate sandwich complexes, analogous to previously prepared related complexes. Spectroscopic characterization points to the stability of these complexes in solution over a reasonably wide pH range. Density functional analysis suggests that the Ce-O bond strength in [Ce(PMo 11O 39) 2] (10-) is greater than the Th-O bond strength in [Th(PMo 11O 39) 2] (10-), with the dominant bonding interaction being ionic in both cases. In contrast, under similar reaction conditions, the dominant solid state Zr (IV) and Hf (IV) complexes formed contain the anions [Zr(PMo 12O 40)(PMo 11O 39)] (6-) and [Hf(PMo 12O 40)(PMo 11O 39)] (6-), respectively. In these complexes the central Group 4 d-block metal cations are coordinated to the four unsaturated terminal lacunary site oxygens of the [PMo 11O 39] (7-) ligand and to four bridging oxygens of a plenary Keggin anion, [PMo 12O 40] (3-). In addition, (NH 4) 5{Hf[PMo 12O 40][(NH 4)PMo 11O 39]}.23.5H 2O can be crystallized as a minor product. The structure of the anion, {Hf[PMo 12O 40][(NH 4)PMo 11O 39]} (5-), reveals coordination of the central Hf (IV) cation via four bridging oxygens on both the coordinated [PMo 11O 39] (7-) and [PMo 12O 40] (3-) anions

  4. Laser Spectroscopy of Small Mass Selected Metal Clusters and Complexes

    NASA Astrophysics Data System (ADS)

    Robbins, David Lee

    1995-01-01

    Analysis and characterization of novel complexes, especially those exhibiting weak bonding, is of fundamental and applied importance. Van der Waals forces and other weak bonding forces have attracted much attention recently due to recognition of their broad impact. Weak forces control solvent-solute interaction, govern reaction channels at large internuclear separations, and play key roles in the geometry and activity of biological macromolecules. Direct study of these phenomena is extremely complex, but much may be learned by the study of small and simplified systems. The most simplified solvation system conceivable consists of a single solute solvated by one solvent ligand. Production and isolation of such weakly bound complexes is difficult owing to their instability and short lifetime in ordinary conditions. Advances in several technologies over the past two decades have facilitated their study. Two of the most notable advancements have been in molecular beam and laser technologies. These advanced technologies as well as fundamental physical chemistry techniques are exploited for the production, isolation, and study of silver dimer solvated by single rare gas adducts, the magnesium cation solvated by one nitrogen molecule, and the unsolvated bimetallic, AlAg. Resonant photoionization and photodissociation techniques are used to explore the potential energy surfaces of these complexes. These studies reveal electronic, vibrational, and rotational energy levels which allow the determination of structure and dissociation energies. Success in these investigations is due largely to the metals chosen. Both silver and magnesium have a low density of electronic states, strong accessible electronic transitions, and are amenable to molecular beam experiments. For similar reasons theoretical investigations of these or similar systems have recently been undertaken and are compared to the experimental work. Both of the van der Waals studies are unique. Neither complex had

  5. Asymmetric Schiff bases derived from diaminomaleonitrile and their metal complexes

    NASA Astrophysics Data System (ADS)

    Yang, Jianjie; Shi, Rufei; Zhou, Pei; Qiu, Qiming; Li, Hui

    2016-02-01

    Asymmetric Schiff bases, due to its asymmetric structure, can be used as asymmetric catalyst, antibacterial, and mimic molecules during simulate biological processes, etc. In recent years, research on synthesis and properties of asymmetric Schiff bases have become an increase interest of chemists. This review summarizes asymmetric Schiff bases derived from diaminomaleonitrile (DAMN) and DAMN-based asymmetric Schiff bases metal complexes. Applications of DAMN-based asymmetric Schiff bases are also discussed in this review.

  6. mer and fac isomerism in tris chelate diimine metal complexes.

    PubMed

    Dabb, Serin L; Fletcher, Nicholas C

    2015-03-14

    In this perspective, we highlight the issue of meridional (mer) and facial (fac) orientation of asymmetrical diimines in tris-chelate transition metal complexes. Diimine ligands have long been the workhorse of coordination chemistry, and whilst there are now good strategies to isolate materials where the inherent metal centered chirality is under almost complete control, and systematic methodologies to isolate heteroleptic complexes, the conceptually simple geometrical isomerism has not been widely investigated. In systems where the two donor atoms are significantly different in terms of the σ-donor and π-accepting ability, the fac isomer is likely to be the thermodynamic product. For the diimine complexes with two trigonal planar nitrogen atoms there is much more subtlety to the system, and external factors such as the solvent, lattice packing and the various steric considerations play a delicate role in determining the observed and isolable product. In this article we discuss the possibilities to control the isomeric ratio in labile systems, consider the opportunities to separate inert complexes and discuss the observed differences in their spectroscopic properties. Finally we report on the ligand orientation in supramolecular systems where facial coordination leads to simple regular structures such as helicates and tetrahedra, but the ability of the ligand system to adopt a mer orientation enables self-assembled structures of considerable beauty and complexity.

  7. Mechanics of metal-catecholate complexes: the roles of coordination state and metal types.

    PubMed

    Xu, Zhiping

    2013-10-10

    There have been growing evidences for the critical roles of metal-coordination complexes in defining structural and mechanical properties of unmineralized biological materials, including hardness, toughness, and abrasion resistance. Their dynamic (e.g. pH-responsive, self-healable, reversible) properties inspire promising applications of synthetic materials following this concept. However, mechanics of these coordination crosslinks, which lays the ground for predictive and rational material design, has not yet been well addressed. Here we present a first-principles study of representative coordination complexes between metals and catechols. The results show that these crosslinks offer stiffness and strength near a covalent bond, which strongly depend on the coordination state and type of metals. This dependence is discussed by analyzing the nature of bonding between metals and catechols. The responsive mechanics of metal-coordination is further mapped from the single-molecule level to a networked material. The results presented here provide fundamental understanding and principles for material selection in metal-coordination-based applications.

  8. Mechanics of metal-catecholate complexes: The roles of coordination state and metal types

    PubMed Central

    Xu, Zhiping

    2013-01-01

    There have been growing evidences for the critical roles of metal-coordination complexes in defining structural and mechanical properties of unmineralized biological materials, including hardness, toughness, and abrasion resistance. Their dynamic (e.g. pH-responsive, self-healable, reversible) properties inspire promising applications of synthetic materials following this concept. However, mechanics of these coordination crosslinks, which lays the ground for predictive and rational material design, has not yet been well addressed. Here we present a first-principles study of representative coordination complexes between metals and catechols. The results show that these crosslinks offer stiffness and strength near a covalent bond, which strongly depend on the coordination state and type of metals. This dependence is discussed by analyzing the nature of bonding between metals and catechols. The responsive mechanics of metal-coordination is further mapped from the single-molecule level to a networked material. The results presented here provide fundamental understanding and principles for material selection in metal-coordination-based applications. PMID:24107799

  9. Half-sandwich iron(ii) complexes with protic acyclic diaminocarbene ligands: synthesis, deprotonation and metalation reactions.

    PubMed

    Ruiz, Javier; García, Lucía; Vivanco, Marilín; Sol, Daniel; García-Granda, Santiago

    2017-08-08

    A variety of half-sandwich iron(ii) complexes with diprotic acyclic diaminocarbene ligands (pADCs) have been obtained by reaction of the cationic complexes [Fe(Cp)(CO)2(CNR)](+) and [Fe(Cp)(CO)(CNR)2](+) with methylamine, and their acid-base behaviour was studied, revealing an easy reversible deprotonation reaction of both N-H moieties of the carbene ligands. The deprotonation process is frequently followed by a nucleophilic attack of the nitrogen atom on a vicinal carbonyl or isocyanide ligand, affording the corresponding metallacycles. Metalation of one or two N-H groups of the pADC ligands can be accomplished by reaction of the carbene complexes with either [AuCl(PPh3)] or [Ru(p-cym)Cl2]2 in the presence of KOH or LiHMDS as deprotonating agents. A number of Fe(ii)/Au(i) and Fe(ii)/Ru(ii) heterometallic complexes have been prepared in this way, some of them formally containing unique metalla-N-heterocyclic carbene ligands.

  10. Metal Complexes And Free Radical Toxins Produced By Pfiesteria Piscicida

    SciTech Connect

    Moeller, P.D.R.; Beauchesne, K.R.; Huncik, K.M.; Davis, W.C.; Christopher, S.J.; Riggs-Gelasco, P.; Gelasco, A.K.

    2009-06-03

    Metal-containing organic toxins produced by Pfiesteria piscicida were characterized, for the first time, by corroborating data obtained from five distinct instrumental methods: nuclear magnetic resonance spectroscopy (NMR), inductively coupled plasma mass spectrometry (ICPMS), liquid chromatography particle beam glow discharge mass spectrometry (LC/PB-GDMS), electron paramagnetic resonance spectroscopy (EPR), and X-ray absorption spectroscopy (XAS). The high toxicity of the metal-containing toxins is due to metal-mediated free radical production. This mode of activity explains the toxicity of Pfiesteria, as well as previously reported difficulty in observing the molecular target, due to the ephemeral nature of radical species. The toxins are highly labile in purified form, maintaining activity for only 2-5 days before all activity is lost. The multiple toxin congeners in active extracts are also susceptible to decomposition in the presence of white light, pH variations, and prolonged heat. These findings represent the first formal isolation and characterization of a radical forming toxic organic-ligated metal complex isolated from estuarine/marine dinoflagellates. These findings add to an increased understanding regarding the active role of metals interacting with biological systems in the estuarine environment, as well as their links and implications to human health.

  11. Metal Complexes and Free Radical Toxins Produced by Pfiesteria piscicida

    SciTech Connect

    Moeller,P.; Beauchesne, K.; Huncik, K.; Davis, W.; Christopher, S.; Riggs-Gelasco, P.; Gelasco, A.

    2007-01-01

    Metal-containing organic toxins produced by Pfiesteria piscicida were characterized, for the first time, by corroborating data obtained from five distinct instrumental methods: nuclear magnetic resonance spectroscopy (NMR), inductively coupled plasma mass spectrometry (ICP-MS), liquid chromatography particle beam glow discharge mass spectrometry (LC/PB-GDMS), electron paramagnetic resonance spectroscopy (EPR), and X-ray absorption spectroscopy (XAS). The high toxicity of the metal-containing toxins is due to metal-mediated free radical production. This mode of activity explains the toxicity of Pfiesteria, as well as previously reported difficulty in observing the molecular target, due to the ephemeral nature of radical species. The toxins are highly labile in purified form, maintaining activity for only 2-5 days before all activity is lost. The multiple toxin congeners in active extracts are also susceptible to decomposition in the presence of white light, pH variations, and prolonged heat. These findings represent the first formal isolation and characterization of a radical forming toxic organic-ligated metal complex isolated from estuarine/marine dinoflagellates. These findings add to an increased understanding regarding the active role of metals interacting with biological systems in the estuarine environment, as well as their links and implications to human health.

  12. Metal complexes and free radical toxins produced by Pfiesteria piscicida.

    PubMed

    Moeller, Peter D R; Beauchesne, Kevin R; Huncik, Kevin M; Davis, W Clay; Christopher, Steven J; Riggs-Gelasco, Pamela; Gelasco, Andrew K

    2007-02-15

    Metal-containing organic toxins produced by Pfiesteria piscicida were characterized, for the first time, by corroborating data obtained from five distinct instrumental methods: nuclear magnetic resonance spectroscopy (NMR), inductively coupled plasma mass spectrometry (ICP-MS), liquid chromatography particle beam glow discharge mass spectrometry (LC/PB-G DMS), electron paramagnetic resonance spectroscopy (EPR), and X-ray absorption spectroscopy (XAS). The high toxicity of the metal-containing toxins is due to metal-mediated free radical production. This mode of activity explains the toxicity of Pfiesteria, as well as previously reported difficulty in observing the molecular target, due to the ephemeral nature of radical species. The toxins are highly labile in purified form, maintaining activity for only 2-5 days before all activity is lost. The multiple toxin congeners in active extracts are also susceptible to decomposition in the presence of white light, pH variations, and prolonged heat. These findings represent the first formal isolation and characterization of a radical forming toxic organic-ligated metal complex isolated from estuarine/marine dinoflagellates. These findings add to an increased understanding regarding the active role of metals interacting with biological systems in the estuarine environment, as well as their links and implications to human health.

  13. Mono, bi- and trinuclear metal complexes derived from new benzene-1,4-bis(3-pyridin-2-ylurea) ligand. Spectral, magnetic, thermal and 3D molecular modeling studies

    NASA Astrophysics Data System (ADS)

    El-ghamry, Mosad A.; Saleh, Akila A.; Khalil, Saied M. E.; Mohammed, Amira A.

    2013-06-01

    New bis (pyridylurea) ligand, H2L, was synthesized by the reaction of ethylpyridine-2-carbamate (EPC) and p-phenylenediamine. The ligand was characterized by elemental analysis, IR, 1H NMR, electronic and mass spectra. Reaction of the prepared ligand with Co2+, Ni2+, Cu2+, Fe3+, VO2+ and UO22+ ions afforded mono, bi- and trinuclear metal complexes. Also, new mixed ligand complexes of the ligand H2L and 8-hydroxyquinoline (8-HQ) with Co2+, Ni2+, Cu2+ and Fe3+ ions were synthesized. The ligand behaves as bi- and tetradentate toward the transition metal ions, coordination via the pyridine sbnd N, the carbonyl sbnd O and/or the amidic sbnd N atoms in a non, mono- and bis-deprotonated form. The complexes were characterized by elemental and thermal analyses, IR, electronic and mass spectra as well as conductance and magnetic susceptibility measurements. The results showed that the metal complexes exhibited different geometrical arrangements such as square planar, tetrahedral, octahedral and square pyramidal arrangements. The Coats-Redfern equation was used to calculate the kinetic and thermodynamic parameters for the different thermal decomposition steps of some complexes. 3D molecular modeling of the ligand, H2L and a representative complex were studied.

  14. (Comparison of group transfer, inner sphere and outer sphere electron transfer mechanisms of organometallic complexes: Progress report)

    SciTech Connect

    Atwood, J.

    1990-01-01

    We have constructed an infrared stopped-flow spectrophotometer and initiated a study of the mechanisms of reactions that involve a change in the oxidation state of organometallic complexes. In this summary we highlight our results on reactions (1) that formally involve exchange of a charged species between two metal carbonyl anions, (2) that involve addition of an electron to, or removal of an electron from organometallic complexes that contain a metal-metal bond, and (3) between coordination complexes and metal carbonyl anions.

  15. [Comparison of group transfer, inner sphere and outer sphere electron transfer mechanisms of organometallic complexes: Progress report

    SciTech Connect

    Atwood, J.

    1990-12-31

    We have constructed an infrared stopped-flow spectrophotometer and initiated a study of the mechanisms of reactions that involve a change in the oxidation state of organometallic complexes. In this summary we highlight our results on reactions (1) that formally involve exchange of a charged species between two metal carbonyl anions, (2) that involve addition of an electron to, or removal of an electron from organometallic complexes that contain a metal-metal bond, and (3) between coordination complexes and metal carbonyl anions.

  16. Late transition metal m-or chemistry and D6 metal complex photoeliminations

    SciTech Connect

    Sharp, Paul

    2015-07-31

    With the goal of understanding and controlling photoreductive elimination reactions from d6 transition metal complexes as part of a solar energy storage cycle we have investigated the photochemistry of Pt(IV) bromo, chloro, hydroxo, and hydroperoxo complexes. Photoreductive elimination reactions occur for all of these complexes and appear to involve initial Pt-Br, Pt-Cl, or Pt-O bond fission. In the case of Pt-OH bond fission, the subsequent chemistry can be controlled through hydrogen bonding to the hydroxo group.

  17. Metal complexes of cyclic tetra-azatetra-acetic acids.

    PubMed

    Delgado, R; da Silva, J J

    1982-10-01

    The cyclic tetra-aza complexones cDOTA ([12]ane N(4).4ac), cTRITA ([13]ane N(4).4ac) and cTETA ([14]ane N(4).4ac) have been synthesized and characterized by elemental analysis, titration, melting-point determination and NMR (and infrared) spectroscopy. The ionization constants and the stability constants of the MH(2)L, MHL and ML complexes formed with alkali, alkaline-earth and some transition metals were determined at 25.0 +/- 0.1 degrees and ionic strength 0.10M [KNO(3) and (CH(3))(4)NNO(3)]. It was confirmed that cDOTA forms the most stable Ca(2+) and Sr(2+) complexes but the reported inversion of the order of stability of the complexes of these two ions with cTRITA was not confirmed. Also, the values of the stability constants determined in this work differ substantially from those previously reported for ML species. cDOTA is an interesting alternative to classical non-cyclic complex-ones for the complexometric determination of Ca(2+) and Mg(2+) but neither this ligand nor the other two offer advantages over EDTA or DCTA for the complexometric titration of transition metals.

  18. Synthesis and cytotoxic activity of metallic complexes of lawsone.

    PubMed

    Oramas-Royo, Sandra; Torrejón, Concepción; Cuadrado, Irene; Hernández-Molina, Rita; Hortelano, Sonsoles; Estévez-Braun, Ana; de Las Heras, Beatriz

    2013-05-01

    In the present study, a series of metallic complexes of the 1,4-naphthoquinone lawsone (2-6) were synthesized and evaluated for potential cytotoxicity in a mouse leukemic macrophagic RAW 264.7 cell line. Cell viability was determined by the MTT assay. Significant growth inhibition was observed for the copper complex (4) with an IC(50) value of 2.5 μM. This compound was selected for further evaluation of cytotoxic activity on several human cancer cells including HT-29 (human colorectal adenocarcinoma), HepG2 (human hepatocellular carcinoma) and HeLa, (human cervical adenocarcinoma cells). Significant cell viability decrease was also observed in HepG2 cells. The apoptotic potential of this complex was evaluated in these cells. Compound 4 induced apoptosis by a mechanism that involves the activation of caspases 3, 8 and 9 and modulation of apoptotic-related proteins such as Bax, Bad, and p53. These results indicate that metal complexes of lawsone derivatives, in particular compound 4, might be used for the design of new antitumoral agents. Copyright © 2013 Elsevier Ltd. All rights reserved.

  19. Synthesis, spectroscopic characterization, electrochemistry and biological evaluation of some metal (II) complexes with ONO donor ligand containing benzo[b]thiophene and coumarin moieties

    NASA Astrophysics Data System (ADS)

    Mahendra Raj, K.; Mruthyunjayaswamy, B. H. M.

    2014-09-01

    Schiff base ligand 3-chloro-N‧-((7-hydroxy-4-methyl-2-oxo-2H-chromen-8-yl)methylene)benzo[b]thiophene-2-carbohydrazide and its Cu(II), Co(II), Ni(II) and Zn(II) complexes were synthesized, characterized by elemental analysis and various physico-chemical techniques like, IR, 1H NMR, ESI-mass, UV-Visible, thermogravimetry - differential thermal analysis, magnetic measurements and molar conductance. Spectral analysis indicates octahedral geometry for all the complexes. Cu(II) complex have 1:1 stoichiometry of the type [M(L)(Cl)(H2O)2], whereas Co(II), Ni(II) and Zn(II) complexes have 1:2 stoichiometric ratio of the type [M(L)2]. The bonding sites are the oxygen atom of amide carbonyl, nitrogen of azomethine function and phenolic oxygen of the Schiff base ligand via deprotonation. The thermogravimetry - differential thermal analysis studies gave evidence for the presence of coordinated water molecules in the composition of Cu(II) complex which was further supported by IR measurements. All the complexes were investigated for their electrochemical activity, but only the Cu(II) complex showed the redox property. In order to evaluate the effect of antimicrobial potency of metal ions upon chelation, ligand and its metal complexes along with their respective metal chlorides were screened for their antibacterial and antifungal activities by minimum inhibitory concentration (MIC) method. The results showed that the metal complexes were found to be more active than free ligand. Ligand and its complexes were screened for free radical scavenging activity by DPPH method and DNA cleavage activity using Calf-thymus DNA (Cat. No-105850).

  20. High-density monolayers of metal complexes: preparation and catalysis.

    PubMed

    Hara, Kenji; Sawamura, Masaya; Fukuoka, Atsushi

    2014-10-01

    Catalysts are one of the key materials for realizing a sustainable society. However, we may encounter problematic cases where conventional catalyst systems cannot provide effective solutions. We thus believe that the establishment of novel methods of catalyst preparation is currently necessary. Utilization of high-density monolayers of molecular metal complexes is our strategy, and we expect that this methodology will enable facile and systematic screening of unique and efficient catalysts. This Personal Account describes our challenges to establish such an immature method in catalyst preparation as well as the related background and perspective. Preparation and catalysis by high-density monolayers of Rh complexes with N-heterocyclic carbene, structurally compact phosphine and diisocyanide ligands on gold surfaces are presented. The catalytic application of a high-density Pd-bisoxazoline complex prepared on a single-crystal silicon surface is also shown. Uniquely high catalyst turnover numbers and high chemoselectivities were observed with these catalyst systems.

  1. Metal–Metal Bonding in Uranium–Group 10 Complexes

    PubMed Central

    2016-01-01

    Heterobimetallic complexes containing short uranium–group 10 metal bonds have been prepared from monometallic IUIV(OArP-κ2O,P)3 (2) {[ArPO]− = 2-tert-butyl-4-methyl-6-(diphenylphosphino)phenolate}. The U–M bond in IUIV(μ-OArP-1κ1O,2κ1P)3M0, M = Ni (3–Ni), Pd (3–Pd), and Pt (3–Pt), has been investigated by experimental and DFT computational methods. Comparisons of 3–Ni with two further U–Ni complexes XUIV(μ-OArP-1κ1O,2κ1P)3Ni0, X = Me3SiO (4) and F (5), was also possible via iodide substitution. All complexes were characterized by variable-temperature NMR spectroscopy, electrochemistry, and single crystal X-ray diffraction. The U–M bonds are significantly shorter than any other crystallographically characterized d–f-block bimetallic, even though the ligand flexes to allow a variable U–M separation. Excellent agreement is found between the experimental and computed structures for 3–Ni and 3–Pd. Natural population analysis and natural localized molecular orbital (NLMO) compositions indicate that U employs both 5f and 6d orbitals in covalent bonding to a significant extent. Quantum theory of atoms-in-molecules analysis reveals U–M bond critical point properties typical of metallic bonding and a larger delocalization index (bond order) for the less polar U–Ni bond than U–Pd. Electrochemical studies agree with the computational analyses and the X-ray structural data for the U–X adducts 3–Ni, 4, and 5. The data show a trend in uranium–metal bond strength that decreases from 3–Ni down to 3–Pt and suggest that exchanging the iodide for a fluoride strengthens the metal–metal bond. Despite short U–TM (transition metal) distances, four other computational approaches also suggest low U–TM bond orders, reflecting highly transition metal localized valence NLMOs. These are more so for 3–Pd than 3–Ni, consistent with slightly larger U–TM bond orders in the latter. Computational studies of the model systems (PH3)3MU(OH)3I

  2. Infrared Spectroscopy of Metal Ion Complexes: Models for Metal Ligand Interactions and Solvation

    NASA Astrophysics Data System (ADS)

    Duncan, Michael

    2006-03-01

    Weakly bound complexes of the form M^+-Lx (M=Fe, Ni, Co, etc.; L=CO2, C2H2, H2O, benzene, N2) are prepared in supersonic molecular beams by laser vaporization in a pulsed-nozzle cluster source. These species are mass analyzed and size-selected in a reflectron time-of-flight mass spectrometer. Clusters are photodissociated at infrared wavelengths with a Nd:YAG pumped infrared optical parametric oscillator/amplifier (OPO/OPA) laser or with a tunable infrared free-electron laser. M^+-(CO2)x complexes absorb near the free CO2 asymmetric stretch near 2349 cm-1 but with an interesting size dependent variation in the resonances. Small clusters have blue-shifted resonances, while larger complexes have additional bands due to surface CO2 molecules not attached to the metal. M^+(C2H2)n complexes absorb near the C-H stretches in acetylene, but resonances in metal complexes are red-shifted with repect to the isolated molecule. Ni^+ and Co^+ complexes with acetylene undergo intracluster cyclization reactions to form cyclobutadiene. Transition metal water complexes are studied in the O-H stretch region, and partial rotational structure can be measured. M^+(benzene) and M^+(benzene)2 ions (M=V, Ti, Al) represent half-sandwich and sandwich species, whose spectra are measured near the free benzene modes. These new IR spectra and their assignments will be discussed as well as other new IR spectra for similar complexes.

  3. Identification of metal species by ESI-MS/MS through release of free metals from the corresponding metal-ligand complexes.

    PubMed

    Tsednee, Munkhtsetseg; Huang, Yu-Chen; Chen, Yet-Ran; Yeh, Kuo-Chen

    2016-05-31

    Electrospray ionization-mass spectrometry (ESI-MS) is used to analyze metal species in a variety of samples. Here, we describe an application for identifying metal species by tandem mass spectrometry (ESI-MS/MS) with the release of free metals from the corresponding metal-ligand complexes. The MS/MS data were used to elucidate the possible fragmentation pathways of different metal-deoxymugineic acid (-DMA) and metal-nicotianamine (-NA) complexes and select the product ions with highest abundance that may be useful for quantitative multiple reaction monitoring. This method can be used for identifying different metal-ligand complexes, especially for metal species whose mass spectra peaks are clustered close together. Different metal-DMA/NA complexes were simultaneously identified under different physiological pH conditions with this method. We further demonstrated the application of the technique for different plant samples and with different MS instruments.

  4. Exploring biologically relevant chemical space with metal complexes.

    PubMed

    Meggers, Eric

    2007-06-01

    Altering biological processes with small synthetic molecules is a general approach for the design of drugs and molecular probes. Medicinal chemistry and chemical biology are focused predominately on the design of organic molecules, whereas inorganic compounds find applications mainly for their reactivity (e.g. cisplatin as a DNA-reactive therapeutic) or imaging properties (e.g. gadolinium complexes as MRI diagnostics). In such inorganic pharmaceuticals or probes, coordination chemistry in the biological environment or at the target site lies at the heart of their modes of action. However, past and very recent results suggest that it is also worth exploring a different aspect of metal complexes: their ability to form structures with unique and defined shapes for the design of 'organic-like' small-molecule probes and drugs. In such metal-organic compounds, the metal has the main purpose to organize the organic ligands in three-dimensional space. It is likely that such an approach will complement the molecular diversity of organic chemistry in the quest for the discovery of compounds with superior biological activities.

  5. 40 CFR 721.4680 - Metal salts of complex inorganic oxyacids (generic name).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Metal salts of complex inorganic... New Uses for Specific Chemical Substances § 721.4680 Metal salts of complex inorganic oxyacids... substances identified generically as metal salts of complex inorganic oxyacids (PMNs P-89-576 and...

  6. 40 CFR 721.4680 - Metal salts of complex inorganic oxyacids (generic name).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Metal salts of complex inorganic... New Uses for Specific Chemical Substances § 721.4680 Metal salts of complex inorganic oxyacids... substances identified generically as metal salts of complex inorganic oxyacids (PMNs P-89-576 and...

  7. 40 CFR 721.4680 - Metal salts of complex inorganic oxyacids (generic name).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Metal salts of complex inorganic... New Uses for Specific Chemical Substances § 721.4680 Metal salts of complex inorganic oxyacids... substances identified generically as metal salts of complex inorganic oxyacids (PMNs P-89-576 and...

  8. 40 CFR 721.4680 - Metal salts of complex inorganic oxyacids (generic name).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Metal salts of complex inorganic... New Uses for Specific Chemical Substances § 721.4680 Metal salts of complex inorganic oxyacids... substances identified generically as metal salts of complex inorganic oxyacids (PMNs P-89-576 and...

  9. ‘New Trends for Metal Complexes with Anticancer Activity’

    PubMed Central

    Bruijnincx, Pieter C. A.; Sadler, Peter J.

    2010-01-01

    Summary Medicinal inorganic chemistry can exploit the unique properties of metal ions for the design of new drugs. This has, for instance, led to the clinical application of chemotherapeutic agents for cancer treatment, such as cisplatin. The use of cisplatin is, however, severely limited by its toxic side effects. This has spurred chemists to employ different strategies in the development of new metal-based anticancer agents with different mechanisms of action. Recent trends in the field are discussed in this review. These include the more selected delivery and/or activation of cisplatin-related prodrugs and the discovery of new non-covalent interactions with the classical target, DNA. The use of the metal as scaffold rather than reactive centre and the departure from the cisplatin paradigm of activity towards a more targeted, cancer cell-specific approach, a major trend, are discussed as well. All this, together with the observation that some of the new drugs are organometallic complexes, illustrates that exciting times lie ahead for those interested in ‘metals in medicine’. PMID:18155674

  10. Ring opening and bidentate coordination of amidinate germylenes and silylenes on carbonyl dicobalt complexes: the importance of a slight difference in ligand volume.

    PubMed

    Cabeza, Javier A; García-Álvarez, Pablo; Pérez-Carreño, Enrique; Polo, Diego

    2014-07-07

    The reactions of [Co2 (CO)8 ] with one equiv of the benzamidinate (R2 bzam) group-14 tetrylenes [M(R2 bzam)(HMDS)] (HMDS=N(SiMe3 )2 ; 1: M=Ge, R=iPr; 2: M=Si, R=tBu; 3: M=Ge, R=tBu) at 20 °C led to the monosubstituted complexes [Co2 {κ(1) MM(R2 bzam)(HMDS)}(CO)7 ] (4: M=Ge, R=iPr; 5: M=Si, R=tBu; 6: M=Ge, R=tBu), which contain a terminal κ(1) M-tetrylene ligand. Whereas the Co2 Si and Co2 Ge tert-butyl derivatives 5 and 6 are stable at 20 °C, the Co2 Ge isopropyl derivative 4 evolved to the ligand-bridged derivative [Co2 {μ-κ(2) Ge,N-Ge(iPr2 bzam)(HMDS)}(μ-CO)(CO)5 ] (7), in which the Ge atom spans the CoCo bond and one arm of the amidinate fragment is attached to a Co atom. The mechanism of this reaction has been modeled with the help of DFT calculations, which have also demonstrated that the transformation of amidinate-tetrylene ligands on the dicobalt framework is negligibly influenced by the nature of the group-14 metal atom (Si or Ge) but is strongly dependent upon the volume of the amidinate NR groups. The disubstituted derivatives [Co2 {κ(1) MM(R2 bzam)(HMDS)}2 (CO)6 ] (8: M=Ge, R=iPr; 9: M=Si, R=tBu; 10: M=Ge, R=tBu), which contain two terminal κ(1) M-tetrylene ligands, have been prepared by treating [Co2 (CO)8 ] with two equiv of 1-3 at 20 °C. The IR spectra of 8-10 have shown that the basicity of germylenes 1 and 3 is very high (comparable to that of trialkylphosphanes and 1,3-diarylimidazol-2-ylidenes), whereas that of silylene 2 is even higher.

  11. Theoretical study of the cycloaddition reaction of a tungsten-containing carbonyl ylide.

    PubMed

    Ito, Kazuta; Hara, Yoshihiro; Mori, Seiji; Kusama, Hiroyuki; Iwasawa, Nobuharu

    2009-11-16

    The [3+2] cycloaddition reaction of a tungsten-containing carbonyl ylide with methyl vinyl ether and the insertion reactions of the nonstabilized carbene complex intermediates produced have been investigated through the use of B3LYP density functional theory. The [3+2] cycloaddition reaction of the tungsten-containing carbonyl ylide has been proven to proceed concertedly, reversibly, and with high endo selectivity. The intermolecular Si-H insertion reactions of the carbene complex intermediates have been proven to be favored over the intramolecular C-H insertion, in good agreement with experimental results. Moreover, the kinetic endo/exo ratio of the [3+2] cycloaddition reaction has been shown to determine the endo/exo selectivity of the Si-H insertion products. In addition, secondary orbital interactions involving the benzene ring and the carbonyl ligand on the metal center have turned out to strongly influence the high endo selectivity of the [3+2] cycloaddition reaction with methyl vinyl ether.

  12. Probing metal ion complexation with salicylic acid and its derivatives with excited state proton transfer and luminescence anisotropy

    SciTech Connect

    Wang, Z.; Friedrich, D.M.; Ainsworth, C.C.

    1996-10-01

    Salicylic acid and its derivatives in which the phenolic proton is preserved show a characteristic dual fluorescence: one band in the UV, due to a {open_quotes}normal{close_quotes} excited state emission, and the other in the visible range, is assigned to excited state intramolecular proton transfer (ESIPT). The transition energy, quantum yield and fluorescence lifetime as well as fluorescence anisotropy are sensitive to the solvent environment, temperature and properties of the substituents (complexation) at the phenolic and carboxylic oxygens. The ESIPT band disappears in molecules in which the intramolecular hydrogen bond between phenolic hydrogen and the carbonyl oxygen is prohibited. In this work, the complexation of Na(I), Ca(II), Al(III) and La(III) with salicylic acid, 3-hydroxybenzoic acid, methylsalicylate and anisic acid in both aqueous and non-aqueous solvents has been studied by absorption and steady state luminescence spectroscopy, picosecond to nanosecond luminescence lifetimes and luminescence anisotropy measurements in a range of solvent and in ethanol at 77 K. Speciation in these complex systems, binding characteristics between the metal ion and the ligand, and ligand-centered energetics are discussed in terms of the spectroscopic properties, luminescence and anisotropy decay kinetics.

  13. Dynamics of tungsten and cobalt carbonyls on silica surfaces

    NASA Astrophysics Data System (ADS)

    Muthukumar, Kaliappan; Valenti, Roser; Jeschke, Harald O.

    2013-03-01

    Metal carbonyl species adsorbed on a substrate are the starting point for the electron beam induced deposition of metallic nanostructures. We employ first principles molecular dynamics simulations to investigate the dynamics of tungsten hexa- and pentacarbonyl as well as cobalt octacarbonyl precursor molecules on fully and partially hydroxylated silica substrates. We find that physisorbed carbonyls are quite mobile on a silica surface saturated with hydroxy groups, moving around half an Angstrom per picosecond. In contrast, chemisorbed ions like [W(CO)5]- or [Co(CO)4]- are more stable at room temperature. We determine the vibrational spectra which can provide signatures for experimentally distinguishing the form in which precursors cover a substrate.

  14. Survey of metal finishing capabilities in the Nuclear Weapons Complex

    SciTech Connect

    Johnson, H.R.; Stoltz, R.E.

    1990-12-01

    This report presents the results of a survey of the metal finishing capabilities of the following design and production agencies in the Nuclear Weapon Complex: Allied Signal Aerospace Co. (AS), General Electric Neutron Device Division (GEND), Los Alamos National Laboratory (LANL), Lawrence Livermore National Laboratory (LLNL), EG&G Mound Applied Technology (MD), EG&G Rocky Flats Plant (RF), Sandia National Laboratories, Albuquerque (SNL, A), Sandia National Laboratories, Livermore (SNL, L) and Martin Marietta Energy Systems, Inc. (Y-12). It defines the current status of electroplating and its allied processes at each of these agencies, the methods and procedures for handling waste, and the major environmental, safety, and health issues confronting metal finishing personnel.

  15. Exciton complexes in low dimensional transition metal dichalcogenides

    SciTech Connect

    Thilagam, A.

    2014-08-07

    We examine the excitonic properties of layered configurations of low dimensional transition metal dichalcogenides (LTMDCs) using the fractional dimensional space approach. The binding energies of the exciton, trion, and biexciton in LTMDCs of varying layers are analyzed, and linked to the dimensionality parameter α, which provides insight into critical electro-optical properties (relative oscillator strength, absorption spectrum, exciton-exciton interaction) of the material systems. The usefulness of α is highlighted by its independence of the physical mechanisms underlying the confinement effects of geometrical structures. Our estimates of the binding energies of exciton complexes for the monolayer configuration of transition metal dichalcogenides suggest a non-collinear structure for the trion and a positronium-molecule-like square structure for the biexciton.

  16. Complex metallic alloys as new materials for additive manufacturing.

    PubMed

    Kenzari, Samuel; Bonina, David; Marie Dubois, Jean; Fournée, Vincent

    2014-04-01

    Additive manufacturing processes allow freeform fabrication of the physical representation of a three-dimensional computer-aided design (CAD) data model. This area has been expanding rapidly over the last 20 years. It includes several techniques such as selective laser sintering and stereolithography. The range of materials used today is quite restricted while there is a real demand for manufacturing lighter functional parts or parts with improved functional properties. In this article, we summarize recent work performed in this field, introducing new composite materials containing complex metallic alloys. These are mainly Al-based quasicrystalline alloys whose properties differ from those of conventional alloys. The use of these materials allows us to produce light-weight parts consisting of either metal-matrix composites or of polymer-matrix composites with improved properties. Functional parts using these alloys are now commercialized.

  17. Complex metal borohydrides: multifunctional materials for energy storage and conversion.

    PubMed

    Mohtadi, Rana; Remhof, Arndt; Jena, Puru

    2016-09-07

    With the limited supply of fossil fuels and their adverse effect on the climate and the environment, it has become a global priority to seek alternate sources of energy that are clean, abundant, and sustainable. While sources such as solar, wind, and hydrogen can meet the world's energy demand, considerable challenges remain to find materials that can store and/or convert energy efficiently. This topical review focuses on one such class of materials, namely, multi-functional complex metal borohydrides that not only have the ability to store sufficient amount of hydrogen to meet the needs of the transportation industry, but also can be used for a new generation of metal ion batteries and solar cells. We discuss the material challenges in all these areas and review the progress that has been made to address them, the issues that still need to be resolved and the outlook for the future.

  18. Pentiptycene-based concave NHC-metal complexes.

    PubMed

    Savka, Roman; Foro, Sabine; Plenio, Herbert

    2016-07-05

    The reaction of 1-amino,4-hydroxy-pentiptycene with diacetyl or acenaphthene-1,2-dione gave the respective diimines, followed by alkylation of the hydroxyl groups, and cyclization of the alkylated diimines to the respective bispentiptycene-imidazolium salts NHC·HCl. The azolium salts, being precursors to N-heterocyclic carbenes, were converted into metal complexes [(NHC)MX] (MX = CuI, AgCl, AuCl) and [(NHC)IrCl(cod)] and [(NHC)IrCl(CO)2] in good yields. In the solid state [(NHC)AgCl] displays a bowl-shaped structure of the ligand with the metal center buried within the concave unit.

  19. Complex metallic alloys as new materials for additive manufacturing

    NASA Astrophysics Data System (ADS)

    Kenzari, Samuel; Bonina, David; Dubois, Jean Marie; Fournée, Vincent

    2014-04-01

    Additive manufacturing processes allow freeform fabrication of the physical representation of a three-dimensional computer-aided design (CAD) data model. This area has been expanding rapidly over the last 20 years. It includes several techniques such as selective laser sintering and stereolithography. The range of materials used today is quite restricted while there is a real demand for manufacturing lighter functional parts or parts with improved functional properties. In this article, we summarize recent work performed in this field, introducing new composite materials containing complex metallic alloys. These are mainly Al-based quasicrystalline alloys whose properties differ from those of conventional alloys. The use of these materials allows us to produce light-weight parts consisting of either metal-matrix composites or of polymer-matrix composites with improved properties. Functional parts using these alloys are now commercialized.

  20. Complex metal borohydrides: multifunctional materials for energy storage and conversion

    NASA Astrophysics Data System (ADS)

    Mohtadi, Rana; Remhof, Arndt; Jena, Puru

    2016-09-01

    With the limited supply of fossil fuels and their adverse effect on the climate and the environment, it has become a global priority to seek alternate sources of energy that are clean, abundant, and sustainable. While sources such as solar, wind, and hydrogen can meet the world’s energy demand, considerable challenges remain to find materials that can store and/or convert energy efficiently. This topical review focuses on one such class of materials, namely, multi-functional complex metal borohydrides that not only have the ability to store sufficient amount of hydrogen to meet the needs of the transportation industry, but also can be used for a new generation of metal ion batteries and solar cells. We discuss the material challenges in all these areas and review the progress that has been made to address them, the issues that still need to be resolved and the outlook for the future.

  1. Heterobimetallic porphyrin complexes displaying triple dynamics: coupled metal motions controlled by constitutional evolution.

    PubMed

    Le Gac, Stéphane; Fusaro, Luca; Roisnel, Thierry; Boitrel, Bernard

    2014-05-07

    A bis-strap porphyrin ligand (1), with an overhanging carboxylic acid group on each side of the macrocycle, has been investigated toward the formation of dynamic libraries of bimetallic complexes with Hg(II), Cd(II), and Pb(II). Highly heteroselective metalation processes occurred in the presence of Pb(II), with Hg(II) or Cd(II) bound out-of-plane to the N-core and "PbOAc" bound to a carboxylate group of a strap on the opposite side. The resulting complexes, 1(Hg)·PbOAc and 1(Cd)·PbOAc, display three levels of dynamics. The first is strap-level (interactional dynamics), where the PbOAc moiety swings between the left and right side of the strap owing to a second sphere of coordination with lateral amide functions. The second is ligand-level (motional dynamics), where 1(Hg)·PbOAc and 1(Cd)·PbOAc exist as two degenerate states in equilibrium controlled by a chemical effector (AcO(-)). The process corresponds to a double translocation of the metal ions according to an intramolecular migration of Hg(II) or Cd(II) through the N-core, oscillating between the two equivalent overhanging carbonyl groups, coupled to an intermolecular pathway for PbOAc exchanging between the two equivalent overhanging carboxylate groups (N-core(up) ⇆ N-core(down) coupled to strap(down) ⇆ strap(up), i.e., coupled motion #1 in the abstract graphic). The third is library-level (constitutional dynamics), where a dynamic constitutional evolution of the system was achieved by the successive addition of two chemical effectors (DMAP and then AcO(-)). It allowed shifting equilibrium forward and backward between 1(Hg)·PbOAc and the corresponding homobimetallic complexes 1(Hg2)·DMAP and 1(Pb)·PbOAc. The latter displays a different ligand-level dynamics, in the form of an intraligand coupled migration of the Pb(II) ions (N-core(up) ⇆ strap(up) coupled to strap(down) ⇆ N-core(down), i.e., coupled motion #2 in the abstract graphic). In addition, the neutral "bridged" complexes 1HgPb and 1Cd

  2. Chemistry and Properties of Complex Intermetallics from Metallic Fluxes

    SciTech Connect

    Kanatzidis, Mercouri G.

    2015-03-28

    This project investigated the reaction chemistry and synthesis of new intermetallic materials with complex compositions and structures using metallic fluxes as solvents. It was found that the metallic fluxes offer several key advantages in facilitating the formation and crystal growth of new materials. The fluxes mostly explored were liquid aluminum, gallium and indium. The main purpose of this project was to exploit the potential of metallic fluxes as high temperature solvent for materials discovery in the broad class of intermetallics. This work opened new paths to compound formation. We discovered many new Si (or Ge)-based compounds with novel structures, bonding and physicochemical properties. We created new insights about the reaction chemistry that is responsible for stabilizing the new materials. We also studied the structural and compositional relationships to understand their properties. We investigated the use of Group-13 metals Al, Ga and In as solvents and have generated a wide variety of new results including several new ternary and quaternary materials with fascinating structures and properties as well as new insights as to how these systems are stabilized in the fluxes. The project focused on reactions of metals from the rare earth element family in combination with transition metals with Si and Ge. For example molten gallium has serves both as a reactive and non-reactive solvent in the preparation and crystallization of intermetallics in the system RE/M/Ga/Ge(Si). Molten indium behaves similarly in that it too is an excellent reaction medium, but it gives compounds that are different from those obtained from gallium. Some of the new phase identified in the aluminide class are complex phases and may be present in many advanced Al-matrix alloys. Such phases play a key role in determining (either beneficially or detrimentally) the mechanical properties of advanced Al-matrix alloys. This project enhanced our basic knowledge of the solid state chemistry

  3. Oxygen activation with transition metal complexes in aqueous solution

    SciTech Connect

    Bakac, Andreja

    2010-04-12

    Coordination to transition-metal complexes changes both the thermodynamics and kinetics of oxygen reduction. Some of the intermediates (superoxo, hydroperoxo, and oxo species) are close analogues of organic oxygen-centered radicals and peroxides (ROO{sm_bullet}, ROOH, and RO{sm_bullet}). Metal-based intermediates are typically less reactive, but more persistent, than organic radicals, which makes the two types of intermediates similarly effective in their reactions with various substrates. The self-exchange rate constant for hydrogen-atom transfer for the couples Cr{sub aq}OO{sup 2+}/Cr{sub aq}OOH{sup 2+} and L{sup 1}(H{sub 2}O)RhOO{sup 2+}/L{sup 1}(H{sub 2}O)RhOOH{sup 2+} was estimated to be 10{sup 1 {+-} 1} M{sup -1} s{sup -1}. The use of this value in the simplified Marcus equation for the Cr{sub aq}O{sup 2+}/Cr{sub aq}OOH{sup 2+} cross reaction provided an upper limit k{sub CrO,CrOH} {le} 10{sup (-2{+-}1)} M{sup -1} s{sup -1} for Cr{sub aq}O{sup 2+}/Cr{sub aq}OH{sup 2+} self-exchange. Even though superoxo complexes react very slowly in bimolecular self-reactions, extremely fast cross reactions with organic counterparts, i.e., acylperoxyl radicals, have been observed. Many of the intermediates generated by the interaction of O{sub 2} with reduced metal complexes can also be accessed by alternative routes, both thermal and photochemical.

  4. A study of fundamental reaction pathways for transition metal alkyl complexes. I. The reaction of a nickel methyl complex with alkynes. Ii. The mechanism of aldehyde formation in the reaction of a molybdenum hydride with molybdenum alkyls

    SciTech Connect

    Huggins, John Mitchell

    1980-06-12

    it was possible to show that the mixed dimers MeCpMo(CO)3-(CO)3MoCp (3b) and MeCpMo(CO)2≡(CO)2 MoCp (4b) are the predominant kinetic products of the reaction. Additionally labeling the carbonyl ligands of 1a with 13CO led to the conclusion that all three of the carbonyl ligands in 1a end up in the tetracarbonyl dimers 4a if the reaction is carried out under a continuous purge of argon Trapping studies failed to find any evidence for the intermediacy of either [CpMo(CO)3] - or [CpMo(CO)3] + in this reaction. A mechanism is proposed that involves the initial migration of the alkyl ligand in 2 to CO forming an unsaturated acyl complex which reacts with 1a to give a binuclear complex containing a three center-two electron Mo-H-Mo bond. This complex then selectively looses a carbonyl from the acyl molybdenum, migrates the hydride to that same metal, and forms a metal-metal bond. This binuclear complex with the hydride and acyl ligands on one metal reductively eliminates aldehyde, and migrates a carbonyl ligand, to give 4a directly. The other product 3a is formed by addition of two molecules of free CO to 4a.

  5. PNP-Pincer-Type Phosphaalkene Complexes of Late Transition Metals.

    PubMed

    Ozawa, Fumiyuki; Nakajima, Yumiko

    2016-10-01

    This account summarizes our recent studies on PNP-pincer-type phosphaalkene complexes. Phosphaalkenes with a P=C bond possess an extremely low-lying π* orbital and have a marked tendency to engage in strong π back-bonding with transition metals. This particular ligand property provides PNP-pincer complexes with unique structures and reactivities. 2,6-Bis(phosphaethenyl)pyridine leads to the isolation of coordinatively unsaturated complexes of Fe(I) and Cu(I); the former adopts a trigonal monopyramidal configuration, whereas the latter has a strong affinity for PF6- and SbF6- as non-coordinating anions. Unsymmetrical PNP-pincer-type phosphaalkene complexes of Ir(I) bearing a dearomatized pyridine unit instantly cleave the N-H bond of NH3 and the C-H bond of MeCN at room temperature. The dearomatized iridium complexes catalyze the dehydrative coupling of amines with alcohols to afford N-alkylated amines and imines in high yields.

  6. Synthesis and luminescence of some rare earth metal complexes

    NASA Astrophysics Data System (ADS)

    Bochkarev, Mikhail N.; Pushkarev, Anatoly P.

    2016-12-01

    In the present paper the synthesis, photoand electroluminescent properties of new rare earth metal complexes prepared and studied at the Razuvaev Institute of Organometallic Chemistry during the last decade are reviewed. The obtained compounds give luminescence in UV, visible and NIR regions. The substituted phenolates, naphtholates, mercaptobenzothiazolate, 8-oxyquinolinolate, polyfluorinated alcoholates and chalcogenophosphinates were used as ligands. The synthesis and structure of unusual three-nuclear sulfidenitride clusters of Nd and Dy are described. The new excitation mechanism of ytterbium phenolates and naphtholates, which includes the stage of reversible reduction of Yb to divalent state and oxidation of the ligands in the excitation process, is discussed.

  7. Dynamic heteroleptic metal-phenanthroline complexes: from structure to function.

    PubMed

    Saha, Manik Lal; Neogi, Subhadip; Schmittel, Michael

    2014-03-14

    Dynamically heteroligated metal centres are auspicious platforms to access multicomponent supramolecular systems, the latter showing unique structures, amazing properties and even emergent functions. The great potential of heteroleptic complexes has materialised after the development of appropriate strategies that warrant quantitative formation in spite of the dynamic character. In this perspective, we discuss our endeavours at developing various heteroleptic self-assembly protocols based on sterically bulky 2,9-diarylphenanthrolines and our work toward self-sorted multicomponent architectures and assemblies with new and useful functions.

  8. Long tailed cage amines: Synthesis, metal complexation, and structure

    SciTech Connect

    Dittrich, Birger; Harrowfield, Jack M.; Koutsantonis, George A.; Nealon, Gareth L.; Skelton, Brian W.

    2011-12-09

    The generation of amphiphiles derived from macrobicyclic hexamines of the 'sarcophagine' class can be prepared through efficient and selective reactions involving the reductive alkylation, using long-chain aldehydes, of amino-functionalized sarcophagines when bound to Cu(II) or Mg(II). The Mg(II) pathway is particularly convenient for the ultimate isolation of the free ligands, which can then be used to form metalloamphiphiles with a variety of metal ions. Structural studies have been made of one of the free (protonated) ligands and some of their complexes.

  9. Rationally designed, polymeric, extended metal-ciprofloxacin complexes.

    PubMed

    Xiao, Dong-Rong; Wang, En-Bo; An, Hai-Yan; Su, Zhong-Min; Li, Yang-Guang; Gao, Lei; Sun, Chun-Yan; Xu, Lin

    2005-11-04

    Reactions of the antimicrobial fluoroquinolone ciprofloxacin (cfH) with metal salts in the presence of aromatic polycarboxylate ligands or under basic conditions produce fourteen new metal-cfH complexes, namely, [Ba2(cf)2(1,4-bdc)(H2O)2] x H2O (1), [Sr6(cf)6(1,4-bdc)3(H2O)6] x 2H2O (2), [M2(cfH)2(bptc)(H2O)2] x 8H2O (M = Mn3 and Cd4), [M(cfH)(1,3-bdc)] (M = Mn5, Co6, and Zn7), [Zn2(cfH)4(1,4-bdc)](1,4-bdc) x 13H2O (8), [Ca(cfH)2(1,2-Hbdc)2] x 2H2O (9) and [M(cf)2] x 2.5H2O (M = Mn10, Co11, Zn12, Cd13, and Mg14) (1,4-bdc = 1,4-benzenedicarboxylate, bptc = 3,3',4,4'-benzophenonetetracarboxylate, 1,3-bdc = 1,3-benzenedicarboxylate, 1,2-bdc = 1,2-benzenedicarboxylate). Their structures were determined by single-crystal X-ray diffraction analyses and further characterized by elemental analyses, IR spectra, and thermogravimetric analyses. The structures of 1 and 2 consist of unique two-dimensional arm-shaped layers. Compounds 3 and 4 are isostructural and feature one-dimensional structures formed from the interconnection of [M2(cfH)2(H2O)2] dimers with bptc ligands. Compounds 5-7 are isostructural and contain double-chain-like ribbons constructed from [M2(cfH)2(CO2)2] dimers and 1,3-bdc. Compound 8 consists of a pair of [Zn(cfH)2]2+ fragments bridged by a 1,4-bdc into a dinuclear dumbbell structure. Compound 9 is a neutral monomeric complex. To the best of our knowledge, compounds 1-9 are the first examples of metal-quinolone complexes that contain aromatic polycarboxylate ligands. Compounds 10-14 are isostructural and exhibit interesting two-dimensional rhombic grids featuring large cavities with dimensions of 13.6x13.6 A. Up to now, polymeric extended metal-cfH complexes have never been reported.

  10. The DNA-binding and bioactivity of rare earth metal complexes.

    PubMed

    Yang, Li; Wang, Bochu; Tan, Jun; Zhu, Liancai

    2013-08-01

    Recently more and more attention is paid to the rare earth metal complexes, because the properties of the rare earth metals are similar to those of the transition metals such as the similar atomic and the ionic radius. A large number of rare metal complexes were synthesized, and their bioactivities were also studied. This review highlights recent researches on the interaction of some rare earth metal complexes with DNA, analyzes how the configuration of the complexes influences the binding affinity, and focuses on the pharmacological activities of the complexes, such as anticancer, antibacterial, antioxidant, anti-inflammatory and anti-virus.

  11. Temporary anion states of. pi. -ligand transition-metal carbonyls studied by means of electron transmission spectroscopy and x. cap alpha. calculations

    SciTech Connect

    Modelli, A.; Distefano, G.; Guerra, M.; Jones, D.

    1987-07-22

    The resonances observed in the electron transmission spectra of (benzene)chromium tricarbonyl, (cyclopentadienyl)manganese tricarbonyl, (1,3-butadiene)iron tricarbonyl, and (cyclopentadienyl)cobalt dicarbonyl have been assigned with the aid of MS X..cap alpha.. calculations. In contrast with previous theoretical results, the present calculations on the neutral states show a large net electronic charge transfer from the ..pi.. ligand to the metal.

  12. Effects of carbonyl bond, metal cluster dissociation, and evaporation rates on predictions of nanotube production in high-pressure carbon monoxide

    NASA Technical Reports Server (NTRS)

    Scott, Carl D.; Smalley, Richard E.

    2003-01-01

    The high-pressure carbon monoxide (HiPco) process for producing single-wall carbon nanotubes (SWNTs) uses iron pentacarbonyl as the source of iron for catalyzing the Boudouard reaction. Attempts using nickel tetracarbonyl led to no production of SWNTs. This paper discusses simulations at a constant condition of 1300 K and 30 atm in which the chemical rate equations are solved for different reaction schemes. A lumped cluster model is developed to limit the number of species in the models, yet it includes fairly large clusters. Reaction rate coefficients in these schemes are based on bond energies of iron and nickel species and on estimates of chemical rates for formation of SWNTs. SWNT growth is measured by the conformation of CO2. It is shown that the production of CO2 is significantly greater for FeCO because of its lower bond energy as compared with that of NiCO. It is also shown that the dissociation and evaporation rates of atoms from small metal clusters have a significant effect on CO2 production. A high rate of evaporation leads to a smaller number of metal clusters available to catalyze the Boudouard reaction. This suggests that if CO reacts with metal clusters and removes atoms from them by forming MeCO, this has the effect of enhancing the evaporation rate and reducing SWNT production. The study also investigates some other reactions in the model that have a less dramatic influence.

  13. Effects of carbonyl bond, metal cluster dissociation, and evaporation rates on predictions of nanotube production in high-pressure carbon monoxide

    NASA Technical Reports Server (NTRS)

    Scott, Carl D.; Smalley, Richard E.

    2003-01-01

    The high-pressure carbon monoxide (HiPco) process for producing single-wall carbon nanotubes (SWNTs) uses iron pentacarbonyl as the source of iron for catalyzing the Boudouard reaction. Attempts using nickel tetracarbonyl led to no production of SWNTs. This paper discusses simulations at a constant condition of 1300 K and 30 atm in which the chemical rate equations are solved for different reaction schemes. A lumped cluster model is developed to limit the number of species in the models, yet it includes fairly large clusters. Reaction rate coefficients in these schemes are based on bond energies of iron and nickel species and on estimates of chemical rates for formation of SWNTs. SWNT growth is measured by the conformation of CO2. It is shown that the production of CO2 is significantly greater for FeCO because of its lower bond energy as compared with that of NiCO. It is also shown that the dissociation and evaporation rates of atoms from small metal clusters have a significant effect on CO2 production. A high rate of evaporation leads to a smaller number of metal clusters available to catalyze the Boudouard reaction. This suggests that if CO reacts with metal clusters and removes atoms from them by forming MeCO, this has the effect of enhancing the evaporation rate and reducing SWNT production. The study also investigates some other reactions in the model that have a less dramatic influence.

  14. Complexing agent and heavy metal removals from metal plating effluent by electrocoagulation with stainless steel electrodes.

    PubMed

    Kabdaşli, Işik; Arslan, Tülin; Olmez-Hanci, Tuğba; Arslan-Alaton, Idil; Tünay, Olcay

    2009-06-15

    In the present study, the treatability of a metal plating wastewater containing complexed metals originating from the nickel and zinc plating process by electrocoagulation using stainless steel electrodes was experimentally investigated. The study focused on the effect of important operation parameters on electrocoagulation process performance in terms of organic complex former, nickel and zinc removals as well as sludge production and specific energy consumption. The results indicated that increasing the applied current density from 2.25 to 9.0 mA/cm(2) appreciably enhanced TOC removal efficiency from 20% to 66%, but a further increase in the applied current density to 56.25 mA/cm(2) did not accelerate TOC removal rates. Electrolyte concentration did not affect the process performance significantly and the highest TOC reduction (66%) accompanied with complete heavy metal removals were achieved at the original chloride content ( approximately 1500 mg Cl/L) of the wastewater sample. Nickel removal performance was adversely affected by the decrease of initial pH from its original value of 6. Optimum working conditions for electrocoagulation of metal plating effluent were established as follows: an applied current density of 9 mA/cm(2), the effluent's original electrolyte concentration and pH of the composite sample. TOC removal rates obtained for all electrocoagulation runs fitted pseudo-first-order kinetics very well (R(2)>92-99).

  15. Kinetic mechanism of pulmonary carbonyl reductase.

    PubMed

    Matsuura, K; Nakayama, T; Nakagawa, M; Hara, A; Sawada, H

    1988-05-15

    The kinetic mechanism of guinea-pig lung carbonyl reductase was studied at pH 7 in the forward reaction with five carbonyl substrates and NAD(P)H and in the reverse reaction with propan-2-ol and NAD(P)+. In each case the enzyme mechanism was sequential, and product-inhibition studies were consistent with a di-iso ordered bi bi mechanism, in which NAD(P)H binds to the enzyme first and NAD(P)+ leaves last and the binding of cofactor induces isomerization. The kinetic and binding studies of the cofactors and several inhibitors such as pyrazole, benzoic acid, Cibacron Blue and benzamide indicate that the cofactor and Cibacron Blue bind to the free enzyme whereas the other inhibitors bind to the binary and/or ternary complexes.

  16. Kinetic mechanism of pulmonary carbonyl reductase.

    PubMed Central

    Matsuura, K; Nakayama, T; Nakagawa, M; Hara, A; Sawada, H

    1988-01-01

    The kinetic mechanism of guinea-pig lung carbonyl reductase was studied at pH 7 in the forward reaction with five carbonyl substrates and NAD(P)H and in the reverse reaction with propan-2-ol and NAD(P)+. In each case the enzyme mechanism was sequential, and product-inhibition studies were consistent with a di-iso ordered bi bi mechanism, in which NAD(P)H binds to the enzyme first and NAD(P)+ leaves last and the binding of cofactor induces isomerization. The kinetic and binding studies of the cofactors and several inhibitors such as pyrazole, benzoic acid, Cibacron Blue and benzamide indicate that the cofactor and Cibacron Blue bind to the free enzyme whereas the other inhibitors bind to the binary and/or ternary complexes. PMID:3048244

  17. Oxidative carbonylation of amines to carbamates

    SciTech Connect

    Waller, F.J.

    1987-04-01

    Within the last several years, new technologies have appeared to replace phosgene for isocyanate manufacture. These include carbamate chemistries based upon dialkyl carbonate, reductive carbonylation of nitroaromatics, and oxidative carbonylation of amines. The carbamate ester can be handled safely and is reversibly cleaved to the isocyanate. The technology described here involves the preparation of both aliphatic and aromatic carbamates from an amine, alcohol, CO, oxidant, and a non-corrosive catalyst. The catalyst precursor is Pd(OAc){sub 2} and the oxidants are copper carboxylates or copper carboxylates and molecular oxygen. The latter represents a one-step carbamate synthesis with high catalyst activity, nearly quantitative conversions and alcohol selectivities greater than 90%. Operating temperatures and pressures are 80-110{degree}C and less than 500 psi, respectively. Experiments designed to probe the mechanism will be presented along with a discussion of novel (Cu(O{sub 2}CR){sub 2}){sub 2}R'NH{sub 2} complexes.

  18. Synthesis of Metal Oxide Particles Using Reaction Route from Rare-Earth Metal-EDTA Complexes

    NASA Astrophysics Data System (ADS)

    Komatsu, Keiji; Tsuchiya, Takaaki; Hasebe, Yasuhiro; Sekiya, Tetsuo; Toyama, Ayumu; Nakamura, Atsushi; Akasaka, Hiroki; Saitoh, Hidetoshi

    2014-06-01

    Highly dense, spherical yttria (Y2O3) and erbia (Er2O3) particles were synthesized from their corresponding metal-ethylenediaminetetraacetic (EDTA) complexes. The EDTA·Y·H and EDTA·Er·H complexes were prepared in powdered form. These complexes were used as the staring materials for synthesis of the Y2O3 and Er2O3 particles. The particles were synthesized using an H2-O2 flame produced with a commercial flame spray apparatus. Crystalline structure, surface and cross-sectional morphologies, and elemental distribution of the synthesized particles were investigated. It was confirmed that the crystalline phases of the Y2O3 and Er2O3 particles were homogeneous. In addition, the elemental distribution of the particles was uniform. These results indicate that dense, spherical particles of Y2O3 and Er2O3 have been synthesized with EDTA·Y·H and EDTA·Er·H complexes, respectively.

  19. Simulation of the mobility of metal-EDTA complexes in groundwater: the influence of contaminant metals.

    PubMed

    Friedly, J C; Kent, D B; Davis, J A

    2002-02-01

    Reactive transport simulations were conducted to model chemical reactions between metal-EDTA (ethylenediaminetetraacetic acid) complexes during transport in a mildly acidic quartz-sand aquifer. Simulations were compared with the results of small-scale tracer tests wherein nickel-, zinc-, and calcium-EDTA complexes and free EDTA were injected into three distinct chemical zones of a plume of sewage-contaminated groundwater. One zone had a large mass of adsorbed, sewage-derived zinc; one zone had a large mass of adsorbed manganese resulting from mildly reducing conditions created by the sewage plume; and one zone had significantly less adsorbed manganese and negligible zinc background. The chemical model assumed that the dissolution of iron(III) from metal-hydroxypolymer coatings on the aquifer sediments by the metal-EDTA complexes was kinetically restricted. All other reactions, including metal-EDTA complexation, zinc and manganese adsorption, and aluminum hydroxide dissolution were assumed to reach equilibrium on the time scale of transport; equilibrium constants were either taken from the literature or determined independently in the laboratory. A single iron(III) dissolution rate constant was used to fit the breakthrough curves observed in the zone with negligible zinc background. Simulation results agreed well with the experimental data in all three zones, which included temporal moments derived from breakthrough curves at different distances downgradient from the injections and spatial moments calculated from synoptic samplings conducted at different times. Results show that the tracer cloud was near equilibrium with respect to Fe in the sediment after 11 m of transport in the Zn-contaminated region but remained far from equilibrium in the other two zones. Sensitivity studies showed that the relative rate of iron(III) dissolution by the different metal-EDTA complexes was less important than the fact that these reactions are rate controlled. Results suggest that

  20. Simulation of the mobility of metal - EDTA complexes in groundwater: The influence of contaminant metals

    USGS Publications Warehouse

    Friedly, J.C.; Kent, D.B.; Davis, J.A.

    2002-01-01

    Reactive transport simulations were conducted to model chemical reactions between metal - EDTA (ethylenediaminetetraacetic acid) complexes during transport in a mildly acidic quartz - sand aquifer. Simulations were compared with the results of small-scale tracer tests wherein nickel-, zinc-, and calcium - EDTA complexes and free EDTA were injected into three distinct chemical zones of a plume of sewage-contaminated groundwater. One zone had a large mass of adsorbed, sewage-derived zinc; one zone had a large mass of adsorbed manganese resulting from mildly reducing conditions created bythe sewage plume; and one zone had significantly less adsorbed manganese and negligible zinc background. The chemical model assumed that the dissolution of iron(III) from metal - hydroxypolymer coatings on the aquifer sediments by the metal - EDTA complexes was kinetically restricted. All other reactions, including metal - EDTA complexation, zinc and manganese adsorption, and aluminum hydroxide dissolution were assumed to reach equilibrium on the time scale of transport; equilibrium constants were either taken from the literature or determined independently in the laboratory. A single iron(III) dissolution rate constant was used to fit the breakthrough curves observed in the zone with negligible zinc background. Simulation results agreed well with the experimental data in all three zones, which included temporal moments derived from breakthrough curves at different distances downgradient from the injections and spatial moments calculated from synoptic samplings conducted at different times. Results show that the tracer cloud was near equilibrium with respect to Fe in the sediment after 11 m of transport in the Zn-contaminated region but remained far from equilibrium in the other two zones. Sensitivity studies showed that the relative rate of iron(III) dissolution by the different metal - EDTA complexes was less important than the fact that these reactions are rate controlled. Results

  1. Protein carbonylation in human diseases.

    PubMed

    Dalle-Donne, Isabella; Giustarini, Daniela; Colombo, Roberto; Rossi, Ranieri; Milzani, Aldo

    2003-04-01

    Oxidative modifications of enzymes and structural proteins play a significant role in the aetiology and/or progression of several human diseases. Protein carbonyl content is the most general and well-used biomarker of severe oxidative protein damage. Human diseases associated with protein carbonylation include Alzheimer's disease, chronic lung disease, chronic renal failure, diabetes and sepsis. Rapid recent progress in the identification of carbonylated proteins should provide new diagnostic (possibly pre-symptomatic) biomarkers for oxidative damage, and yield basic information to aid the establishment an efficacious antioxidant therapy.

  2. Targeting Reactive Carbonyl Species with Natural Sequestering Agents.

    PubMed

    Hwang, Sung Won; Lee, Yoon-Mi; Aldini, Giancarlo; Yeum, Kyung-Jin

    2016-02-27

    Reactive carbonyl species generated by the oxidation of polyunsaturated fatty acids and sugars are highly reactive due to their electrophilic nature, and are able to easily react with the nucleophilic sites of proteins as well as DNA causing cellular dysfunction. Levels of reactive carbonyl species and their reaction products have been reported to be elevated in various chronic diseases, including metabolic disorders and neurodegenerative diseases. In an effort to identify sequestering agents for reactive carbonyl species, various analytical techniques such as spectrophotometry, high performance liquid chromatography, western blot, and mass spectrometry have been utilized. In particular, recent advances using a novel high resolution mass spectrometry approach allows screening of complex mixtures such as natural products for their sequestering ability of reactive carbonyl species. To overcome the limited bioavailability and bioefficacy of natural products, new techniques using nanoparticles and nanocarriers may offer a new attractive strategy for increased in vivo utilization and targeted delivery of bioactives.

  3. Externally controlled spin state switching in metal-organic complexes.

    NASA Astrophysics Data System (ADS)

    Bagrets, Alexei; Meded, Velimir; Ruben, Mario; Evers, Ferdinand

    2009-03-01

    Recent transport experiments have demonstrated that a manipulation of the charge of individual molecules is feasible using electromigrated metal junctions [1] or electrochemical gates in conjunction with the STM [2]. Using elaborated density functional theory calculations, we will discuss a possibility to induce -- by means of charging or applied stress -- a switching between low and high spin states in certain metal-organic systems, [Fe(bpp)2]^2+ (bpp: bispyrazolyl pyridine) and [Mn(tpy)2]^2+ (tpy: terpyridine). Based upon a recent success of the single molecular conduction experiment through Ru(II) complex [3], we anticipate the transport properties of Fe(II) and Mn(II) complexes to be gate controlled via exploiting their spin degree of freedom. [1] E. A. Osorio et al., J. Phys.: Condens. Matter20, 374121 (2008); [2] F. Chen el al., Ann. Rev. Phys. Chem. 58, 535 (2007); Li et al., Nanotechnology 18, 044018 (2007). [3] M. Ruben, A. Landa, E. L"ortscher, H. Riel, M. Mayor, H. G"orls, H. Weber, A. Arnold, and F. Evers, Small (online), DOI: 10.1002/smll.200800390 (2008).

  4. The problems of detecting hydrides in metal carbonyl clusters by 1H NMR: the case study of [H4-n Ni22(C2)4(CO)28(CdBr)2]n- (n = 2-4).

    PubMed

    Bernardi, Alessandro; Femoni, Cristina; Iapalucci, Maria Carmela; Longoni, Giuliano; Zacchini, Stefano

    2009-06-07

    The new tetra-acetylide carbonyl clusters [H(4-n)Ni(22)(C(2))(4)(CO)(28)(CdBr)(2)](n-) (n = 2-4) have been prepared by reacting [Ni(10)C(2)(CO)(15)](2-) with a large excess of CdBr(2).xH(2)O and the molecular structure of the di-anion [H(2)Ni(22)(C(2))(4)(CO)(28)(CdBr)(2)](2-) has been fully elucidated by means of X-ray crystallography. The corresponding [HNi(22)(C(2))(4)(CO)(28)(CdBr)(2)](3-) and [Ni(22)(C(2))(4)(CO)(28)(CdBr)(2)](4-) conjugated bases are quantitatively obtained upon dissolution of [H(2)Ni(22)(C(2))(4)(CO)(28)(CdBr)(2)](2-) salts in more basic solvents such as acetonitrile and DMSO, respectively. The hydride nature of both [H(2)Ni(22)(C(2))(4)(CO)(28)(CdBr)(2)](2-) and [HNi(22)(C(2))(4)(CO)(28)(CdBr)(2)](3-) has been directly proved by (1)H NMR spectroscopy. Their resonances are very broad under all experimental conditions and their chemical shift greatly depends on solvent as well as temperature. Observation of the hydride resonances in [H(4-n)Ni(22)(C(2))(4)(CO)(28)(CdBr)(2)](n-) (n = 2, 3) makes these clusters a case study of the phenomena behind the loss of any NMR signal in higher-nuclearity metal carbonyl cluster anions (MCCA). In the attempt to obtain a better insight on this experimental spectroscopic behaviour, solutions of [NMe(4)](3)[HNi(22)(C(2))(4)(CO)(28)(CdBr)(2)] have been investigated by dynamic light scattering (DLS) at various concentrations. The DLS experiments point out the presence in solution of a distribution of particles with nominal hydrodynamic diameters enormously greater than those of the free cluster ions resulting, probably, from aggregation in solution. This could formally justify the observed NMR behaviour, even if the present observations are preliminary and their quantitative assessment requires further systematic studies on MCCA aggregation in solution.

  5. Influence of the contact metal on the performance of n-type carbonyl-functionalized quaterthiophene organic thin-film transistors

    SciTech Connect

    Schols, S.; Willigenburg, L. van; Mueller, R.; Bode, D.; Debucquoy, M.; Jonge, S. de; Genoe, J.; Heremans, P.

    2008-12-29

    Organic thin-film transistors using 5, 5-diperfluorohexylcarbonyl-2,2:5,2:5,2-quaterthiophene (DFHCO-4T) as the electron conducting organic semiconductor are fabricated and the performance of these transistors with different top-contact metals is investigated. Transistors with Au source-drain top contacts attain an apparent saturation mobility of 4.6 cm{sup 2}/V s, whereas this parameter is 100 times lower for similar transistors with Al/LiF top contacts. We explain this lower performance by the formation of a thin interfacial layer with poor charge injection properties resulting from a redox reaction between Al and DFHCO-4T.

  6. Intraparticulate Metal Speciation Analysis of Soft Complexing Nanoparticles. The Intrinsic Chemical Heterogeneity of Metal-Humic Acid Complexes.

    PubMed

    Town, Raewyn M; van Leeuwen, Herman P

    2016-11-03

    The counterion condensation-Donnan (CCD) model for the electrostatic features of soft, charged nanoparticles (NPs) is applied to the determination of the intrinsic stability constants, K̅int, for inner-sphere Cd(II) and Cu(II) complexes with humic acid NPs. The novel CCD model accounts for the strong ion condensation potential for higher valency counterions within the intraparticulate double layer zone of the soft NP. The approach offers new insights into the intrinsic heterogeneity of the HA complexes, as revealed by the intraparticulate speciation as a function of the true degree of inner-sphere complexation, θM. The ensuing intrinsic heterogeneity parameters, Γ, for CdHA and CuHA complexes are in very good agreement with those obtained from dynamic electrochemical stripping chronopotentiometric measurements. The overall intraparticulate metal ion speciation is found to depend on θM: at low θM the strong inner-sphere complexes predominate whereas at higher θM values, electrically condensed M may be an equally significant or even larger fraction of the particle-associated M.

  7. The impact of metal transport processes on bioavailability of free and complex metal ions in methanogenic granular sludge.

    PubMed

    Bartacek, Jan; Fermoso, Fernando G; Vergeldt, Frank; Gerkema, Edo; Maca, Josef; van As, Henk; Lens, Piet N L

    2012-01-01

    Bioavailability of metals in anaerobic granular sludge has been extensively studied, because it can have a major effect on metal limitation and metal toxicity to microorganisms present in the sludge. Bioavailability of metals can be manipulated by bonding to complexing molecules such as ethylenediaminetetraacetate (EDTA) or diethylenetriaminepentaacetate (DTPA). It has been shown that although the stimulating effect of the complexed metal species (e.g. [CoEDTA](2-)) is very fast, it is not sustainable when applied to metal-limited continuously operated reactors. The present paper describes transport phenomena taking place inside single methanogenic granules when the granules are exposed to various metal species. This was done using magnetic resonance imaging (MRI). The MRI results were subsequently related to technological observations such as changes in methanogenic activity upon cobalt injection into cobalt-limited up-flow anaerobic sludge blanket (UASB) reactors. It was shown that transport of complexed metal species is fast (minutes to tens of minutes) and complexed metal can therefore quickly reach the entire volume of the granule. Free metal species tend to interact with the granular matrix resulting in slower transport (tens of minutes to hours) but higher final metal concentrations.

  8. Studies of Transition Metal Complexes Using Dynamic NMR Techniques.

    NASA Astrophysics Data System (ADS)

    Coston, Timothy Peter John

    Available from UMI in association with The British Library. This Thesis is primarily concerned with the quantitative study of fluxional processes in, predominantly platinum(IV) complexes, with the ligands 1,1,2,2-tetrakis(methylthio)ethane (MeS)_2CHCH(SMe)_2 , and 1,1,2,2-tetrakis(methylthio)ethene (MeS) _2C=C(SMe)_2. Quantitative information relating to the energetics of these processes has been obtained by a combination of one- and two-dimensional NMR techniques. Chapter One provides an introduction to the background of fluxional processes in transition metal complexes together with data concerning the energetics of the processes that have already been studied by NMR techniques. Chapter Two provides a thorough grounding in NMR techniques, in particular those concerned with the quantitative measurement of rates involved in chemical exchange processes. A description of the use of 2D EXSY NMR spectroscopy in obtaining rate data is given. The properties of the magnetic isotope of platinum are given in Chapter Three. A general survey is also given of some additional compounds that have already been studied by platinum-195 spectroscopy. Chapter Four is concerned with the quantitative study of low temperature (<293 K) fluxionality (sulphur inversion) in the complexes (PtXMe_3 (MeS)_2CHCH(SMe) _2) (X = Cl, Br, I). These complexes were studied by dynamic nuclear magnetic resonance and the information regarding the rates of sulphur inversion was obtained by complete band-shape analysis. Chapter Five is concerned with high temperature (>333 K) fluxionality, of the previous complexes, as studied by a combination of one- and two -dimensional NMR techniques. Aside from obtaining thermodynamic parameters for all the processes, a new novel mechanism is proposed. Chapter Six is primarily concerned with the NMR investigation of the new dinuclear complexes ((PtXMe _3)_2(MeS) _2CHCH(SMe)_2) (X = Cl, Br, I). The solution properties have been established and thermo-dynamic parameters

  9. Biodegradable polymer-metal complexes for gene and drug delivery.

    PubMed

    Hosseinkhani, Hossein; Hosseinkhani, Mohsen

    2009-01-01

    The delivery of genes and drugs into cells has increasingly attracted attention for the generation of genetically engineered cells. Successful drug delivery will have enormous academic, clinical, and practical impacts on gene therapy, cell and molecular biology, pharmaceutical and food industries, and bio-production. The major aim of gene therapy is to deliver genetic materials into cells effectively, genetically modifying and repairing cell functions with the possibility of inducing therapeutic healing of disease. The genetic material includes DNA, RNA, antisense, decoy DNA, and ribozymes. The aim is that the appropriate transfection would allow diseased cells to return to a healthy condition. The genetic manipulation is often manifested in the mechanisms of intracellular actions of genes and proteins, and may play an important role in making clear the key genes associated with various diseases. Based on fundamental and scientific knowledge, the delivery technology of genetic material should be applicable to producing various proteins of pharmaceutical value (e.g. cytokines, growth factors, and antibodies) and also to producing seeds resistant to harmful insects and cold weather damage. This implies that the cells might be enhanced to produce valuable pharmaceutical and food products. For each approach, it is important, for successful gene expression, to select an appropriate gene to be delivered as well as to develop the gene delivery technology to enhance transfection efficiency. This review will provide an overview of the enhanced gene expression of plasmid DNA complexed with new non-viral gene delivery vehicles by biodegradable biopolymer-metal complex, introducing our recent research data to emphasize the technical feasibility of biopolymer-metal complexes in gene therapy and biotechnology.

  10. 1,5-asymmetric induction of chirality using pi-allyltricarbonyliron lactone complexes: highly diastereoselective synthesis of alpha-functionalised carbonyl compounds.

    PubMed

    Hollowood, Christopher J; Ley, Steven V; Wright, Edward A

    2003-09-21

    Silyl enol ethers derived from ketone functionalised rho-allyltricarbonyliron lactone complexes undergo highly diastereoselective carbon-fluorine and carbon-oxygen bond formation reactions with excellent control at the alpha-stereogenic centre.

  11. Composite of liposome and metal complexes: Toward creating a new chemical reaction space

    NASA Astrophysics Data System (ADS)

    Koshiyama, Tomomi; Ohba, Masaaki

    2015-12-01

    The purpose of our research is to construct a novel functional space by fixation of various metal complexes into the liposome space. For the functionalization of liposome surface, we designed lipophilic metal complexes and succeeded in the fixation of various metal complexes such as oxidation catalysts. In addition, reactivities of metal complexes on the liposome surface were optimized by controlling their surrounding environment using various types of phospholipids. Furthermore, we succeeded in the incorporation of coordination polymers in inner water phase of liposomes using antibiotic ion channel, and the composites showed absorption of metal ions through antibiotic ion channels.

  12. 49 CFR 173.198 - Nickel carbonyl.

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... 49 Transportation 2 2011-10-01 2011-10-01 false Nickel carbonyl. 173.198 Section 173.198... Nickel carbonyl. (a) Nickel carbonyl must be packed in specification steel or nickel cylinders as prescribed for any compressed gas except acetylene. A cylinder used exclusively for nickel carbonyl may...

  13. 49 CFR 173.198 - Nickel carbonyl.

    Code of Federal Regulations, 2012 CFR

    2012-10-01

    ... 49 Transportation 2 2012-10-01 2012-10-01 false Nickel carbonyl. 173.198 Section 173.198... Nickel carbonyl. (a) Nickel carbonyl must be packed in specification steel or nickel cylinders as prescribed for any compressed gas except acetylene. A cylinder used exclusively for nickel carbonyl may...

  14. 49 CFR 173.198 - Nickel carbonyl.

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... 49 Transportation 2 2013-10-01 2013-10-01 false Nickel carbonyl. 173.198 Section 173.198... Nickel carbonyl. (a) Nickel carbonyl must be packed in specification steel or nickel cylinders as prescribed for any compressed gas except acetylene. A cylinder used exclusively for nickel carbonyl may...

  15. 49 CFR 173.198 - Nickel carbonyl.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... 49 Transportation 2 2010-10-01 2010-10-01 false Nickel carbonyl. 173.198 Section 173.198... Nickel carbonyl. (a) Nickel carbonyl must be packed in specification steel or nickel cylinders as prescribed for any compressed gas except acetylene. A cylinder used exclusively for nickel carbonyl may...

  16. 49 CFR 173.198 - Nickel carbonyl.

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ... 49 Transportation 2 2014-10-01 2014-10-01 false Nickel carbonyl. 173.198 Section 173.198... Nickel carbonyl. (a) Nickel carbonyl must be packed in specification steel or nickel cylinders as prescribed for any compressed gas except acetylene. A cylinder used exclusively for nickel carbonyl may...

  17. Frustration across the periodic table: heterolytic cleavage of dihydrogen by metal complexes.

    PubMed

    Bullock, R Morris; Chambers, Geoffrey M

    2017-08-28

    This perspective examines frustrated Lewis pairs (FLPs) in the context of heterolytic cleavage of H2 by transition metal complexes, with an emphasis on molecular complexes bearing an intramolecular Lewis base. FLPs have traditionally been associated with main group compounds, yet many reactions of transition metal complexes support a broader classification of FLPs that includes certain types of transition metal complexes with reactivity resembling main group-based FLPs. This article surveys transition metal complexes that heterolytically cleave H2, which vary in the degree that the Lewis pairs within these systems interact. Many of the examples include complexes bearing a pendant amine functioning as the base with the metal functioning as the hydride acceptor. Consideration of transition metal compounds in the context of FLPs can inspire new innovations and improvements in transition metal catalysis.This article is part of the themed issue 'Frustrated Lewis pair chemistry'. © 2017 The Author(s).

  18. Oligomeric rare-earth metal cluster complexes with endohedral transition metal atoms

    SciTech Connect

    Steinberg, Simon; Zimmermann, Sina; Brühmann, Matthias; Meyer, Eva; Rustige, Christian; Wolberg, Marike; Daub, Kathrin; Bell, Thomas; Meyer, Gerd

    2014-11-15

    Comproportionation reactions of rare-earth metal trihalides (RX{sub 3}) with the respective rare-earth metals (R) and transition metals (T) led to the formation of 22 oligomeric R cluster halides encapsulating T, in 19 cases for the first time. The structures of these compounds were determined by single-crystal X-ray diffraction and are composed of trimers ((T{sub 3}R{sub 11})X{sub 15}-type, P6{sub 3}/m), tetramers ((T{sub 4}R{sub 16})X{sub 28}(R{sub 4}) (P-43m), (T{sub 4}R{sub 16})X{sub 20} (P4{sub 2}/nnm), (T{sub 4}R{sub 16})X{sub 24}(RX{sub 3}){sub 4} (I4{sub 1}/a) and (T{sub 4}R{sub 16})X{sub 23} (C2/m) types of structure) and pentamers ((Ru{sub 5}La{sub 14}){sub 2}Br{sub 39}, Cc) of (TR{sub r}){sub n} (n=2–5) clusters. These oligomers are further enveloped by inner (X{sup i}) as well as outer (X{sup a}) halido ligands, which possess diverse functionalities and interconnect like oligomers through i–i, i–a and/or a–i bridges. The general features of the crystal structures for these new compounds are discussed and compared to literature entries as well as different structure types with oligomeric T centered R clusters. Dimers and tetramers originating from the aggregation of (TR{sub 6}) octahedra via common edges are more frequent than trimers and pentamers, in which the (TR{sub r}) clusters share common faces. - Graphical abstract: Rare earth-metal cluster complexes with endohedral transition metal atoms (TR{sub 6}) may connect via common edges or faces to form dimers, trimers, tetramers and pentamers of which the tetramers are the most prolific. Packing effects and electron counts play an important role. - Highlights: • Rare-earth metal cluster complexes encapsulate transition metal atoms. • Oligomers are built via connection of octahedral clusters via common edges or faces. • Dimers through pentamers with closed structures are known. • Tetramers including a tetrahedron of endohedral atoms are the most prolific.

  19. Synthesis, spectroscopic characterisation, DNA cleavage, superoxidase dismutase activity and antibacterial properties of some transition metal complexes of a novel bidentate Schiff base derived from isatin and 2-aminopyrimidine.

    PubMed

    Nitha, L P; Aswathy, R; Mathews, Niecy Elsa; Kumari, B Sindhu; Mohanan, K

    2014-01-24

    Complexes of manganese(II), cobalt(II), nickel(II), copper(II) and zinc(II) with a Schiff base, formed by the condensation of isatin with 2-aminopyrimidine have been synthesised and characterised through elemental analysis, molar conductance measurements, magnetic susceptibility, IR, UV-Vis, (1)HNMR, FAB mass and EPR spectral studies. The spectral data revealed that the ligand acts as neutral bidentate, coordinating to the metal ion through the carbonyl oxygen and azomethine nitrogen. Molar conductance values adequately support the electrolytic nature of the complexes. On the basis of the above observations the complexes have been formulated as [M(ISAP)2]X2, where M=Mn(II), Co(II), Ni(II), Cu(II) and Zn(II); X=Cl, OAc; ISAP=2-[N-indole-2-one]aminopyrimidine. The ligand and copper(II) complex were subjected to X-ray diffraction studies. The DNA cleavage study was monitored by gel electrophoresis method. The superoxide dismutase (SOD) mimetic activities of the ligand and the metal complexes were checked using NBT assay. The in vitro antibacterial activity of the synthesized compounds has been tested against gram negative and gram positive bacteria.

  20. Synthesis, spectroscopic characterisation, DNA cleavage, superoxidase dismutase activity and antibacterial properties of some transition metal complexes of a novel bidentate Schiff base derived from isatin and 2-aminopyrimidine

    NASA Astrophysics Data System (ADS)

    Nitha, L. P.; Aswathy, R.; Mathews, Niecy Elsa; Sindhu kumari, B.; Mohanan, K.

    2014-01-01

    Complexes of manganese(II), cobalt(II), nickel(II), copper(II) and zinc(II) with a Schiff base, formed by the condensation of isatin with 2-aminopyrimidine have been synthesised and characterised through elemental analysis, molar conductance measurements, magnetic susceptibility, IR, UV-Vis, 1HNMR, FAB mass and EPR spectral studies. The spectral data revealed that the ligand acts as neutral bidentate, coordinating to the metal ion through the carbonyl oxygen and azomethine nitrogen. Molar conductance values adequately support the electrolytic nature of the complexes. On the basis of the above observations the complexes have been formulated as [M(ISAP)2]X2, where M = Mn(II), Co(II), Ni(II), Cu(II) and Zn(II); X = Cl, OAc; ISAP = 2-[N-indole-2-one]aminopyrimidine. The ligand and copper(II) complex were subjected to X-ray diffraction studies. The DNA cleavage study was monitored by gel electrophoresis method. The superoxide dismutase (SOD) mimetic activities of the ligand and the metal complexes were checked using NBT assay. The in vitro antibacterial activity of the synthesized compounds has been tested against gram negative and gram positive bacteria.

  1. Synthesis, characterization and antimicrobial activities of mixed ligand transition metal complexes with isatin monohydrazone Schiff base ligands and heterocyclic nitrogen base

    NASA Astrophysics Data System (ADS)

    Devi, Jai; Batra, Nisha

    2015-01-01

    Mixed ligand complexes of Co(II), Ni(II), Cu(II) and Zn(II) with various uninegative tridentate ligands derived from isatin monohydrazone with 2-hydroxynapthaldehyde/substituted salicylaldehyde and heterocyclic nitrogen base 8-hydroxyquinoline have been synthesized and characterized by elemental analysis, conductometric studies, magnetic susceptibility and spectroscopic techniques (IR, UV-VIS, NMR, mass and ESR). On the basis of these characterizations, it was revealed that Schiff base ligands existed as monobasic tridentate ONO bonded to metal ion through oxygen of carbonyl group, azomethine nitrogen and deprotonated hydroxyl oxygen and heterocyclic nitrogen base 8-hydroxyquinoline existed as monobasic bidentate ON bonded through oxygen of hydroxyl group and nitrogen of quinoline ring with octahedral or distorted octahedral geometry around metal ion. All the compounds have been tested in vitro against various pathogenic Gram positive bacteria, Gram negative bacteria and fungi using different concentrations (25, 50, 100, 200 μg/mL) of ligands and their complexes. Comparative study of antimicrobial activity of ligands, and their mixed complexes indicated that complexes exhibit enhanced activity as compared to free ligands and copper(II) Cu(LIV)(Q)ṡH2O complex was found to be most potent antimicrobial agent.

  2. The Tolman electronic parameter (TEP) and the metal-metal electronic communication in ditopic NHC complexes.

    PubMed

    Gusev, Dmitry G; Peris, Eduardo

    2013-05-28

    Whereas the electronic communication between metals in dimetallic organometallic compounds is often assessed through cyclic voltammetric measurements, we have found that the variations in the Tolman electronic parameter (TEP) can also be an alternative and effective way of determining this type of interaction. The TEP values of several (CO)3Ni-NHC-X systems with five different ditopic NHC ligand systems [triazolyldiylidene (A), bis(imidazolylidene) (B), benzobis(imidazolylidene) (C), cyclopenta[f,g]acenaphthylenebis(imidazolylidene) (D) and bis(imidazolidinylidene) (F)] were determined by means of DFT calculations. Based on these values, the electron-withdrawing character of the X metal fragments employed in this study was found to increase in the order IrCp(CO) → RhCl(COD) → Ni(CO)3 → Cr(CO)5 → RhCl(CO)2. We found that the degree of electronic interaction through the ditopic NHC ligands is the strongest in A, followed by B and F, while being weak in B and C. The TEP values and the quantitative analysis of the upper molecular orbitals of A and F and their (CO)3Ni-NHC-Ni(CO)3 complexes strongly suggest that the principal electronic interaction between the metal centres of the M-NHC-M' complexes is of σ-type, via the delocalized HOMO and HOMO - 1 orbitals of the NHC ligands.

  3. Hydrogen storage and evolution catalysed by metal hydride complexes.

    PubMed

    Fukuzumi, Shunichi; Suenobu, Tomoyoshi

    2013-01-07

    The storage and evolution of hydrogen are catalysed by appropriate metal hydride complexes. Hydrogenation of carbon dioxide by hydrogen is catalysed by a [C,N] cyclometalated organoiridium complex, [Ir(III)(Cp*)(4-(1H-pyrazol-1-yl-κN(2))benzoic acid-κC(3))(OH(2))](2)SO(4) [Ir-OH(2)](2)SO(4), under atmospheric pressure of H(2) and CO(2) in weakly basic water (pH 7.5) at room temperature. The reverse reaction, i.e., hydrogen evolution from formate, is also catalysed by [Ir-OH(2)](+) in acidic water (pH 2.8) at room temperature. Thus, interconversion between hydrogen and formic acid in water at ambient temperature and pressure has been achieved by using [Ir-OH(2)](+) as an efficient catalyst in both directions depending on pH. The Ir complex [Ir-OH(2)](+) also catalyses regioselective hydrogenation of the oxidised form of β-nicotinamide adenine dinucleotide (NAD(+)) to produce the 1,4-reduced form (NADH) under atmospheric pressure of H(2) at room temperature in weakly basic water. In weakly acidic water, the complex [Ir-OH(2)](+) also catalyses the reverse reaction, i.e., hydrogen evolution from NADH to produce NAD(+) at room temperature. Thus, interconversion between NADH (and H(+)) and NAD(+) (and H(2)) has also been achieved by using [Ir-OH(2)](+) as an efficient catalyst and by changing pH. The iridium hydride complex formed by the reduction of [Ir-OH(2)](+) by H(2) and NADH is responsible for the hydrogen evolution. Photoirradiation (λ > 330 nm) of an aqueous solution of the Ir-hydride complex produced by the reduction of [Ir-OH(2)](+) with alcohols resulted in the quantitative conversion to a unique [C,C] cyclometalated Ir-hydride complex, which can catalyse hydrogen evolution from alcohols in a basic aqueous solution (pH 11.9). The catalytic mechanisms of the hydrogen storage and evolution are discussed by focusing on the reactivity of Ir-hydride complexes.

  4. Infrared multiple photon dissociation spectroscopy of group I and group II metal complexes with Boc-hydroxylamine.

    PubMed

    Dain, Ryan P; Gresham, Gary; Groenewold, Gary S; Steill, Jeffrey D; Oomens, Jos; Van Stipdonk, Michael J

    2013-08-30

    Hydroxamates are essential growth factors for some microbes, acting primarily as siderophores that solubilize iron for transport into a cell. Here we determined the intrinsic structure of 1:1 complexes between Boc-protected hydroxylamine and group I ([M(L)](+)) and group II ([M(L-H)](+)) cations, where M and L are the cation and ligand, respectively, which are convenient models for the functional unit of hydroxamate siderphores. The relevant complex ions were generated by electrospray ionization (ESI) and isolated and stored in a Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometer. Infrared spectra of the isolated complexes were collected by monitoring (infrared) photodissociation yield as a function of photon energy. Experimental spectra were then compared to those predicted by density functional theory (DFT) calculations. The infrared multiple photon dissociation (IRMPD) spectra collected are in good agreement with those predicted to be lowest-energy by DFT. The spectra for the group I complexes contain six resolved absorptions that can be attributed to amide I and II type and hydroxylamine N-OH vibrations. Similar absorptions are observed for the group II cation complexes, with shifts of the amide I and amide II vibrations due to the change in structure with deprotonation of the hydroxylamine group. IRMPD spectroscopy unequivocally shows that the intrinsic binding mode for the group I cations involves the O atoms of the amide carbonyl and hydroxylamine groups of Boc-hydroxylamine. A similar binding mode is preferred for the group II cations, except that in this case the metal ion is coordinated by the O atom of the deprotonated hydroxylamine group. Copyright © 2013 John Wiley & Sons, Ltd.

  5. Complexities of high temperature metal fatigue: Some steps toward understanding

    NASA Technical Reports Server (NTRS)

    Manson, S. S.; Halford, G. R.

    1983-01-01

    After pointing out many of the complexities that attend high temperature metal fatigue beyond those already studied in the sub-creep range, a description of the micromechanisms of deformation and fracture is presented for several classes of materials that were studied over the past dozen years. Strainrange Partitioning (SRP) is used as a framework for interpreting the results. Several generic types of behavior were observed with regard both to deformation and fracture and each is discussed in the context of the micromechanisms involved. Treatment of cumulative fatigue damage and the possibility of ""healing'' of damage in successive loading loops, has led to a new interpretation of the Interaction Damage Rule of SRP. Using the concept of ""equivalent micromechanistic damage'' -- that the same damage on a microscopic scale is induced if the same hysteresis loops are generated, element for element -- it turns out the Interaction Damage Rule essentially compounds a number of variants of hysteresis loops, all of which have the same damage according to SRP concepts, into a set of loops each containing only one of the generic SRP strainranges. Thus the damage associcated with complex loops comprising several types of strainrange is analyzed by considering a combination of loops each containing only one type of strainrange. This concept is expanded to show how several independent loops can combine to ""heal'' creep damage in a complex loading history.

  6. Unusual DNA binding modes for metal anticancer complexes

    PubMed Central

    Pizarro, Ana M.; Sadler, Peter J.

    2010-01-01

    DNA is believed to be the primary target for many metal-based drugs. For example, platinum-based anticancer drugs can form specific lesions on DNA that induce apoptosis. New platinum drugs can be designed that have novel modes of interaction with DNA, such as the trinuclear platinum complex BBR3464. Also it is possible to design inert platinum(IV) pro-drugs which are non-toxic in the dark, but lethal when irradiated with certain wavelengths of light. This gives rise to novel DNA lesions which are not as readily repaired as those induced by cisplatin, and provides the basis for a new type of photoactivated chemotherapy. Finally, newly emerging ruthenium(II) organometallic complexes not only bind to DNA coordinatively, but also by H-bonding and hydrophibic interactions triggered by the introduction of extended arene rings into their versatile structures. Intriguingly osmium (the heavier congener of ruthenium) reacts differently with DNA but can also give rise to highly cytotoxic organometallic complexes. PMID:19344743

  7. N-heterocyclic carbene catalyzed direct carbonylation of dimethylamine.

    PubMed

    Li, Xiaonian; Liu, Kun; Xu, Xiaoliang; Ma, Lei; Wang, Hong; Jiang, Dahao; Zhang, Qunfeng; Lu, Chunshan

    2011-07-21

    N-Heterocyclic carbene (NHC) catalyzed direct carbonylation of dimethylamine leading to the formation of DMF was successfully accomplished under metal-free conditions. The catalytic efficiency was investigated and the turnover numbers can reach as high as >300. The possible mechanism was also proposed.

  8. Effects of solvent induced modulation of energy gaps on electronic relaxation of excited hydrogen bonded complexes of some aromatic carbonyl compounds

    NASA Astrophysics Data System (ADS)

    van der Burgt, M. J.; Jansen, L. M. G.; Huizer, A. H.; Varma, C. A. G. O.

    1995-12-01

    A detailed study of the influence of solvent polarity and temperature dependence ( T ≤ 300 K) on the radiationless transitions of hydrogen bonded complexes of 2-naphthaldehyde ( 1), 2-acetonaphthone ( 2), methyl 2-naphthoate ( 3) and 1,2-dihydro-3H-benz[ e]inden-3-one ( 4) is presented. The hydrogen bonded complexes are strongly fluorescent. The energy gaps between S 1 and S 0 and between S 1 and T 1 could be varied by using various 1,4-dioxane/water mixtures as the solvent. In the case of the complex of 1 intersystem crossing and internal conversion from S 1 have both been found to proceed through a direct process as well as by way of a proces involving thermal excitation to S 2. The conversion of S 1 to T 1 proceeds only through thermal excitation to S 2 in the case of 2 and 4, whereas in the case of 3 a contribution from a thermally activated process could not be detected. An inverse exponential energy gap law has been found for the temperature independent intersystem crossing from S 1 in the case of the complexes of 1 and 3. This is shown theoretically to be in accordance with a nuclear tunneling process. The tunneling appears to proceed along the C-O stretching mode. The internal conversion from the state S 1 of the complex of 3 satisfies the regular exponential energy gap law.

  9. Evaluation of DNA-binding, DNA cleavage, antioxidant and cytotoxic activity of mononuclear ruthenium(II) carbonyl complexes of benzaldehyde 4-phenyl-3-thiosemicarbazones

    NASA Astrophysics Data System (ADS)

    Sampath, Krishnan; Sathiyaraj, Subbaiyan; Jayabalakrishnan, Chinnasamy

    2013-11-01

    Two 4-phenyl-3-thiosemicarbazone ligands, (E)-2-(2-chlorobenzylidene)-N-phenylhydrazinecarbothioamide (HL1) and (E)-2-(2-nitrobenzylidene)-N-phenylhydrazinecarbothioamide (HL2), and its ruthenium(II) complexes were synthesized and characterized by physico-chemical and spectroscopic methods. The Schiff bases act as bidentate, monobasic chelating ligands with S and N as the donor sites and are preferably found in the thiol form in all the complexes studied. The molecular structure of HL1 and HL2 were determined by single crystal X-ray diffraction method. DNA binding of the compounds was investigated by absorption spectroscopy which indicated that the compounds bind to DNA via intercalation. The oxidative cleavage of the complexes with CT-DNA inferred that the effects of cleavage are dose dependent. Antioxidant study of the ligands and complexes showed significant antioxidant activity against DPPH radical. In addition, the in vitro cytotoxicity of the ligands and complexes assayed against HeLa and MCF-7 cell lines showed higher cytotoxic activity with the lower IC50 values indicating their efficiency in killing the cancer cells even at low concentrations.

  10. Dihydrogen bonding vs metal-σ interaction in complexes between H2 and metal hydride.

    PubMed

    Alkorta, Ibon; Elguero, Jose; Solimannejad, Mohammad; Grabowski, Sławomir J

    2011-01-20

    The complexes formed by hydrogen with metal hydrides (LiH, NaH, BeH(2), MgH(2), BH(3), AlH(3), Li(2)H(2), Na(2)H(2), Be(2)H(4), and Mg(2)H(4)) have been theoretically studied at the MP2/aug-cc-pVTZ, MP2/aug-cc-pVQZ and CCSD(T)/aug-cc-pVTZ//CCSD/aug-cc-pVTZ levels of theory. The hydrogen molecule can act as a Lewis acid or base. In the first case, a dihydrogen bonded complex is obtained and in the second an interaction between the σ-bond of the hydrogen molecule and an empty orbital of the metal atoms is found. Quantum theory of atoms in molecules and natural bond orbitals methods have been applied to analyze the intermolecular interactions. Additionally, the cooperativity effects are analyzed for selected complexes with two H(2) molecules where both kinds of interactions exist simultaneously.

  11. Photochemical reactions of metal nitrosyl complexes. Mechanisms of NO reactions with biologically relevant metal centers

    DOE PAGES

    Ford, Peter C.

    2001-01-01

    Tmore » he discoveries that nitric oxide (a.k.a. nitrogen monoxide) serves important roles in mammalian bioregulation and immunology have stimulated intense interest in the chemistry and biochemistry of NO and derivatives such as metal nitrosyl complexes. Also of interest are strategies to deliver NO to biological targets on demand. One such strategy would be to employ a precursor which displays relatively low thermal reactivity but is photochemically active to release NO.his proposition led us to investigate laser flash and continuous photolysis kinetics of nitrosyl complexes such as the Roussin's iron-sulfur-nitrosyl cluster anions Fe 2 S 2 ( NO ) 4 2 − and Fe 4 S 3 ( NO ) 7 − and several ruthenium salen and porphyrin nitrosyls.hese include studies using metal-nitrosyl photochemistry as a vehicle for delivering NO to hypoxic cell cultures in order to sensitize γ -radiation damage. Also studied were the rates and mechanisms of NO “on” reactions with model water soluble heme compounds, the ferriheme protein met-myoglobin and various ruthenium complexes using ns laser flash photolysis techniques. An overview of these studies is presented.« less

  12. Electron spin resonance of radicals and metal complexes

    NASA Astrophysics Data System (ADS)

    The materials are a collection of extended synopsis of papers presented at the conference sessions. The broad area of magnetic technique applications has been described as well as their spectra interpretation methods. The ESR, NMR, ENDOR, and spin echo were applied for studying the radiation and UV induced radicals in chemical and biological systems. Also in the study of complexes of metallic ions (having the paramagnetic properties) and their interaction with the matrix, the magnetic techniques have been commonly used. They are also very convenient tool for the study of reaction kinetics and mechanism as well as interaction of paramagnetic species with themselves and crystal lattice or with the surface as for the catalytic processes.

  13. Acetohydroxamic Acid Complexes with Trivalent f-Block Metal Cations

    SciTech Connect

    Sinkov, Serguei I.; Choppin, Gregory

    2003-11-01

    Acetohydroxamic acid has been studied by optical absorbance spectroscopy as a complex forming reagent for the lighter trivalent lanthanides and actinides (Pu(III) and Am(III)) in aqueous solution at 2.0 M (NaClO4) ionic strength. The highest stoichiometry in all the cases studied has been found to be a 1:4 metal-to-ligand ratio; formation of tetrahydroxamato species requires a high excess of the ligand and alkaline pH, Spectrophotometric monitoring confirmed the presence of Pu(III) by electrochemical reduction of Pu(IV) in the course of the pH titration experiment. The formation constants can be used for optimization of processing flowsheets in the advanced PUREX process.

  14. Complex metallic alloys as new materials for additive manufacturing

    PubMed Central

    Kenzari, Samuel; Bonina, David; Marie Dubois, Jean; Fournée, Vincent

    2014-01-01

    Additive manufacturing processes allow freeform fabrication of the physical representation of a three-dimensional computer-aided design (CAD) data model. This area has been expanding rapidly over the last 20 years. It includes several techniques such as selective laser sintering and stereolithography. The range of materials used today is quite restricted while there is a real demand for manufacturing lighter functional parts or parts with improved functional properties. In this article, we summarize recent work performed in this field, introducing new composite materials containing complex metallic alloys. These are mainly Al-based quasicrystalline alloys whose properties differ from those of conventional alloys. The use of these materials allows us to produce light-weight parts consisting of either metal–matrix composites or of polymer–matrix composites with improved properties. Functional parts using these alloys are now commercialized. PMID:27877661

  15. Friction and solid-solid adhesion on complex metallic alloys

    PubMed Central

    Dubois, Jean-Marie; Belin-Ferré, Esther

    2014-01-01

    The discovery in 1987 of stable quasicrystals in the Al–Cu–Fe system was soon exploited to patent specific coatings that showed reduced friction in ambient air against hard antagonists. Henceforth, it was possible to develop a number of applications, potential or commercially exploited to date, that will be alluded to in this topical review. A deeper understanding of the characteristics of complex metallic alloys (CMAs) may explain why material made of metals like Al, Cu and Fe offers reduced friction; low solid–solid adhesion came later. It is linked to the surface energy being significantly lower on those materials, in which translational symmetry has become a weak property, that is determined by the depth of the pseudo-gap at the Fermi energy. As a result, friction is anisotropic in CMAs that builds up according to the translation symmetry along one direction, but is aperiodic along the other two directions. A review is given in this article of the most salient data found along these lines during the past two decades or so. PMID:27877675

  16. Copper dynamics in doped metal-bis(histidine) complexes.

    PubMed

    Colaneri, Michael J; Vitali, Jacqueline

    2014-07-03

    Electron paramagnetic resonance (EPR) temperature-dependent measurements were undertaken on three Cu(II)-doped metal-histidine complexes to assess copper site dynamic behavior. Previous single-crystal EPR analysis on two of these, zinc d,l-histidine pentahydrate (ZnDLH) and bis(l-histidinato)cadmium dihydrate (CdLH), found that doped Cu(2+) can be modeled as hopping between two neighboring conformational states, with a temperature-dependent rate becoming large enough at room temperature to produce an "averaged" spectrum. By comparing spectra from their powdered form, we show that Cu(2+) doped into a third system, Cd(2+)-d,l-histidine (CdDLH), also exhibits temperature-dependent EPR with features indicating a similar motional-averaging process. In addition, the change of g and copper hyperfine parameters from low to high temperature for CdDLH resembles that in ZnDLH, whereas the change in these parameters for CdLH is like that found in a fourth copper-doped system, zinc l-histidine dihydrate (ZnLH). Taken together, these results suggest that averaging motion between neighboring copper sites is common in metal-bis(histidine) compounds. More detailed studies on biological models are thus warranted, especially because they reveal unique relationships between structure, dynamic processes, and stability and can lead to a better understanding of the role played by site flexibility in copper proteins.

  17. Ring-opening insertion of a substituted dithiazole-3-thione into the Re-Re bond in a dirhenium carbonyl complex

    SciTech Connect

    Adams, R.D.; Huang, M.

    1996-04-16

    The reaction of the complex Re{sub 2}(CO){sub 9}(NCMe) with 5-((ethoxycarbonyl)amino)-1,2,4-dithiazole-3-thione (1) has yielded the series of complexes Re(CO){sub 4}[{mu}-S{sub 2}CNC(N(H)CO{sub 2}Et)S]Re(CO){sub 5} (2; 8% yield), Re(CO){sub 4}[{mu}-S{sub 2}CNC(NHCO{sub 2}Et)S]Re(CO){sub 4} (3; 14% yield), and Re(CO){sub 4}[{mu}-S{sub 2}CNHC(NCO{sub 2}Et)S]Re(CO){sub 4} (4; 27% yield) by the ring-opening insertion of 1 into the rhenium-rhenium bond of Re{sub 2}(CO){sub 9}(NCMe). The sulfur-sulfur bond in 1 was also cleaved. Two mononuclear rhenium complexes, Re(CO){sub 4}[S{sub 2}CNHCSNH(CO{sub 2}Et)] (5; 14% yield) and Re(CO){sub 4}[SCNC(NHCO{sub 2}Et)SCSN] (6; 6% yield), were also isolated and characterized. Compounds 3 and 4 are isomers that exist in an equilibrium at room temperature. The isomerization of 3 to 4 and vice versa is catalyzed by the presence of pyridine. Each of the complexes 2-6 as well as the starting material 1 was characterized by a single-crystal X-ray diffraction analysis. 16 refs., 6 figs., 3 tabs.

  18. Rovibrational Spectroscopy of Aluminum Carbonyl Clusters in Helium Nanodroplets

    NASA Astrophysics Data System (ADS)

    Liang, T.; Morrison, A. M.; Flynn, S. D.; Douberly, G. E.

    2011-06-01

    Helium nanodroplet isolation and a tunable quantum cascade laser are used to probe the fundamental CO stretch bands of Aluminum Carbonyl complexes, Al-(CO)N (n ≤ 5). The droplets are doped with single aluminum atoms via the resistive heating of an aluminum wetted tantalum wire. The downstream sequential pick-up of CO molecules leads to the rapid formation and cooling of Al-(CO)N clusters within the droplets. Near 1900 Cm-1, rotational fine structure is resolved in bands that are assigned to the CO stretch of a 2Π1/2 linear Al-CO species, and the asymmetric and symmetric CO stretch vibrations of a planar C2v Al-(CO)2 complex in a 2B1 electronic state. Bands corresponding to clusters with n ≥ 3 lack resolved rotational fine structure; nevertheless, the small frequency shifts from the n=2 bands indicate that these clusters consist of an Al-(CO)2 core with additional CO molecules attached via van-der-Waals interactions. A second n=2 band is observed near the CO stretch of Al-CO, indicating a local minimum on the n=2 potential consisting of an ``unreacted" Al-CO-(CO) cluster. The linewidth of this band is ˜0.5 cm-1, which is over 50 times broader than transitions within the Al-CO band. The additional broadening is consistent with a homogeneous mechanism corresponding to a rapid vibrational excitation induced reaction within the Al-CO-(CO) cluster to form the covalently bonded Al-(CO)2 complex. For the n=1,2 complexes, CCSD(T) calculations and Natural Bond Orbital (NBO) analyses are carried out to investigate the nature of the bonding in these complexes. The NBO calculations show that both π ``back" donation (from the occupied aluminum p-orbital into the π antibonding CO orbital) and σ donation (from CO into the empty aluminum p-orbitals) play a significant role in the bonding, analogous to transition metal carbonyl complexes. The large redshift of the CO stretch vibrations is consistent with this bonding analysis.

  19. The Effect of Complex Formation upon the Redox Potentials of Metallic Ions. Cyclic Voltammetry Experiments.

    ERIC Educational Resources Information Center

    Ibanez, Jorge G.; And Others

    1988-01-01

    Describes experiments in which students prepare in situ soluble complexes of metal ions with different ligands and observe and estimate the change in formal potential that the ion undergoes upon complexation. Discusses student formation and analysis of soluble complexes of two different metal ions with the same ligand. (CW)

  20. The Effect of Complex Formation upon the Redox Potentials of Metallic Ions. Cyclic Voltammetry Experiments.

    ERIC Educational Resources Information Center

    Ibanez, Jorge G.; And Others

    1988-01-01

    Describes experiments in which students prepare in situ soluble complexes of metal ions with different ligands and observe and estimate the change in formal potential that the ion undergoes upon complexation. Discusses student formation and analysis of soluble complexes of two different metal ions with the same ligand. (CW)

  1. Metal-metal interactions in linear tri-, penta-, hepta-, and nona-nuclear ruthenium string complexes.

    PubMed

    Niskanen, Mika; Hirva, Pipsa; Haukka, Matti

    2012-05-01

    Density functional theory (DFT) methodology was used to examine the structural properties of linear metal string complexes: [Ru(3)(dpa)(4)X(2)] (X = Cl(-), CN(-), NCS(-), dpa = dipyridylamine(-)), [Ru(5)(tpda)(4)Cl(2)], and hypothetical, not yet synthesized complexes [Ru(7)(tpta)(4)Cl(2)] and [Ru(9)(ppta)(4)Cl(2)] (tpda = tri-α-pyridyldiamine(2-), tpta = tetra-α-pyridyltriamine(3-), ppta = penta-α-pyridyltetraamine(4-)). Our specific focus was on the two longest structures and on comparison of the string complexes and unsupported ruthenium backboned chain complexes, which have weaker ruthenium-ruthenium interactions. The electronic structures were studied with the aid of visualized frontier molecular orbitals, and Bader's quantum theory of atoms in molecules (QTAIM) was used to study the interactions between ruthenium atoms. The electron density was found to be highest and distributed most evenly between the ruthenium atoms in the hypothetical [Ru(7)(tpta)(4)Cl(2)] and [Ru(9)(ppta)(4)Cl(2)] string complexes.

  2. Main Group Lewis Acid-Mediated Transformations of Transition-Metal Hydride Complexes.

    PubMed

    Maity, Ayan; Teets, Thomas S

    2016-08-10

    This Review highlights stoichiometric reactions and elementary steps of catalytic reactions involving cooperative participation of transition-metal hydrides and main group Lewis acids. Included are reactions where the transition-metal hydride acts as a reactant as well as transformations that form the metal hydride as a product. This Review is divided by reaction type, illustrating the diverse roles that Lewis acids can play in mediating transformations involving transition-metal hydrides as either reactants or products. We begin with a discussion of reactions where metal hydrides form direct adducts with Lewis acids, elaborating the structure and dynamics of the products of these reactions. The bulk of this Review focuses on reactions where the transition metal and Lewis acid act in cooperation, and includes sections on carbonyl reduction, H2 activation, and hydride elimination reactions, all of which can be promoted by Lewis acids. Also included is a section on Lewis acid-base secondary coordination sphere interactions, which can influence the reactivity of hydrides. Work from the past 50 years is included, but the majority of this Review focuses on research from the past decade, with the intent of showcasing the rapid emergence of this field and the potential for further development into the future.

  3. Synthesis of Ruthenium Carbonyl Complexes with Phosphine or Substituted Cp Ligands, and Their Activity in the Catalytic Deoxygenation of 1,2-Propanediol

    SciTech Connect

    Ghosh, Prasenjit; Fagan, Paul J.; Marshall, William J.; Hauptman, Elisabeth; Bullock, R. Morris

    2009-07-20

    A ruthenium hydride with a bulky substituted Cp ligand, (CpiPr4)Ru(CO)2H (CpiPr4 = C5(i-C3H7)4H) was prepared from the reaction of Ru3(CO)12 with 1,2,3,4-tetraisopropylcyclopentadiene. The molecular structure of (CpiPr4)Ru(CO)2H was determined by x-ray crystallography. The ruthenium hydride complex (C5Bz5)Ru(CO)2H (Bz = CH2Ph) was similarly prepared. The Ru-Ru bonded dimer, [(1,2,3-trimethylindenyl)Ru(CO)2]2, was produced from the reaction of 1,2,3-trimethylindene with Ru3(CO)12, and protonation of this dimer with HOTf gives {[(1,2,3-trimethylindenyl)Ru(CO)2]2(μ H)}+OTf –. A series of ruthenium hydride complexes CpRu(CO)(L)H [L = P(OPh)3, PCy3, PMe3, P(p C6H4F)3] were prepared by reaction of Cp(CO)2RuH with added L. Protonation of (CpiPr4)Ru(CO)2H, Cp*Ru(CO)2H or CpRu(CO)[P(OPh)3]H by HOTf 80 °C led to equilibria with the cationic dihydrogen complexes, but H2 was released at higher temperatures. Protonation of CpRu[P(OPh)3]2H with HOTf gave an observable dihydrogen complex, {CpRu[P(OPh)3]2(η2 H2)}+OTf – that was converted at -20 °C to the dihydride complex {CpRu[P(OPh)3]2(H)2}+OTf –. These Ru complexes serve as catalyst precursors for the catalytic deoxygenation of 1,2-propanediol to give n-propanol. The catalytic reactions were carried out in sulfolane solvent with added HOTf under H2 (750 psi) at 110 °C. This work was supported by the U.S. Department of Energy's (DOE) Office of Basic Energy Sciences, Chemical Sciences program. Pacific Northwest National Laboratory is operated by Battelle for DOE.

  4. Synthesis of Ruthenium Carbonyl Complexes with Phosphine or Substituted Cp Ligands, and Their Activity in the Catalytic Deoxygenation of 1,2-Propanediol

    SciTech Connect

    Bullock, R.M.; Ghosh, P.; Fagan, P.J.; Marshall, W.J.; Hauptman, E.

    2009-07-20

    A ruthenium hydride with a bulky tetra-substituted Cp ligand, (Cp{sup iPr{sub 4}})Ru(CO){sub 2}H (Cp{sup iPr{sub 4}} = C{sub 5}(i-C{sub 3}H{sub 7}){sub 4}H) was prepared from the reaction of Ru{sub 3}(CO){sub 12} with 1,2,3,4-tetraisopropylcyclopentadiene. The molecular structure of (Cp{sup iPr{sub 4}})Ru(CO){sub 2}H was determined by X-ray crystallography. The ruthenium hydride complex (C{sub 5}Bz{sub 5})Ru(CO){sub 2}H (Bz = CH{sub 2}Ph) was similarly prepared. The Ru-Ru bonded dimer, [(1,2,3-trimethylindenyl)Ru(CO){sub 2}]{sub 2}, was produced from the reaction of 1,2,3-trimethylindene with Ru{sub 3}(CO){sub 12}, and protonation of this dimer with HOTf gives {l_brace}[(1,2,3-trimethylindenyl)Ru(CO){sub 2}]{sub 2}-({mu}-H){r_brace}{sup +}OTf{sup -}. A series of ruthenium hydride complexes CpRu(CO)(L)H [L = P(OPh){sub 3}, PCy{sub 3}, PMe{sub 3}, P(p-C{sub 6}H{sub 4}F){sub 3}] were prepared by reaction of Cp(CO){sub 2}RuH with added L. Protonation of (Cp{sup iPr{sub 4}})Ru(CO){sub 2}H, Cp*Ru(CO){sub 2}H, or CpRu(CO)[P-(OPh){sub 3}]H by HOTf at -80 C led to equilibria with the cationic dihydrogen complexes, but H{sub 2} was released at higher temperatures. Protonation of CpRu[P(OPh){sub 3}]{sub 2}H with HOTf gave an observable dihydrogen complex, {l_brace}CpRu[P-(OPh){sub 3}]{sub 2}({eta}{sup 2}-H{sub 2}){r_brace}+OTf{sup -} that was converted at -20 C to the dihydride complex {l_brace}CpRu[P(OPh){sub 3}]{sub 2}(H){sub 2}{r_brace}{sup +}OTf{sup -}. These Ru complexes serve as catalyst precursors for the catalytic deoxygenation of 1,2-propanediol to give n-propanol. The catalytic reactions were carried out in sulfolane solvent with added HOTf under H{sub 2} (750 psi) at 110 C.

  5. Edge-bridging and face-capping coordination of alkenyl ligands in triruthenium carbonyl cluster complexes derived from hydrazines: synthetic, structural, theoretical, and kinetic studies.

    PubMed

    Cabeza, Javier A; del Río, Ignacio; Fernández-Colinas, José M; García-Granda, Santiago; Martínez-Méndez, Lorena; Pérez-Carreño, Enrique

    2004-12-03

    The reactions of the triruthenium cluster complex [Ru3(mu-H)(mu3-eta2-HNNMe2)(CO)9] (1; H2NNMe2=1,1-dimethylhydrazine) with alkynes (PhC triple bond CPh, HC triple bond CH, MeO2CC triple bond CCO2Me, PhC triple bond CH, MeO2CC triple bond CH, HOMe2CC triple bond CH, 2-pyC triple bond CH) give trinuclear complexes containing edge-bridging and/or face-capping alkenyl ligands. Whereas the edge-bridged products are closed triangular species (three Ru-Ru bonds), the face-capped products are open derivatives (two Ru-Ru bonds). For terminal alkynes, products containing gem (RCCH2) and/or trans (RHCCH) alkenyl ligands have been identified in both edge-bridging and face-capping positions, except for the complex [Ru3(mu3-eta2-HNNMe2)(mu3-eta3-HCCH-2-py)(mu-CO)(CO)7], which has the two alkenyl H atoms in a cis arrangement. Under comparable reaction conditions (1:1 molar ratio, THF at reflux, time required for the consumption of complex 1), some reactions give a single product, but most give mixtures of isomers (not all the possible ones), which were separated. To determine the effect of the hydrazido ligand, the reactions of [Ru3(mu-H)(mu3-eta2-MeNNHMe)(CO)9] (2; HMeNNHMe=1,2-dimethylhydrazine) with PhC triple bond CPh, PhC triple bond CH, and HC triple bond CH were also studied. For edge-bridged alkenyl complexes, the Ru--Ru edge that is spanned by the alkenyl ligand depends on the position of the methyl groups on the hydrazido ligand. For face-capped alkenyl complexes, the relative orientation of the hydrazido and alkenyl ligands also depends on the position of the methyl groups on the hydrazido ligand. A kinetic analysis of the reaction of 1 with PhC[triple chemical bond]CPh revealed that the reaction follows an associative mechanism, which implies that incorporation of the alkyne in the cluster is rate-limiting and precedes the release of a CO ligand. X-ray diffraction, IR and NMR spectroscopy, and calculations of minimum-energy structures by DFT methods were used to

  6. Resonant Ultrasound Studies of Complex Transition Metal Oxides

    SciTech Connect

    Dr. Henry Bass; Dr. J. R. Gladden

    2008-08-18

    Department of Energy EPSCoR The University of Mississippi Award: DE-FG02-04ER46121 Resonant Ultrasound Spectroscopy Studies of Complex Transition Metal Oxides The central thrust of this DOE funded research program has been to apply resonant ultrasound spectroscopy (RUS), an elegant and efficient method for determining the elastic stiffness constants of a crystal, to the complex and poorly understood class of materials known as transition metal oxides (TMOs). Perhaps the most interesting and challenging feature of TMOs is their strongly correlated behavior in which spin, lattice, and charge degrees of freedom are strongly coupled. Elastic constants are a measure of the interatomic potentials in a crystal and are thus sensitive probes into the atomic environment. This sensitivity makes RUS an ideal tool to study the coupling of phase transition order parameters to lattice strains. The most significant result of the project has been the construction of a high temperature RUS apparatus capable of making elastic constant measurements at temperatures as high as 1000 degrees Celsius. We have designed and built novel acoustic transducers which can operate as high as 600 degrees Celsius based on lithium niobate piezoelectric elements. For measurement between 600 to 1000 C, a buffer rod system is used in which the samples under test and transducers are separated by a rod with low acoustic attenuation. The high temperature RUS system has been used to study the charge order (CO) transition in transition metal oxides for which we have discovered a new transition occurring about 35 C below the CO transition. While the CO transition exhibits a linear coupling between the strain and order parameter, this new precursor transition shows a different coupling indicating a fundamentally different mechanism. We have also begun a study, in collaboration with the Jet Propulsion Laboratory, to study novel thermoelectric materials at elevated temperatures. These materials include silicon

  7. Understanding atomistic phenomenon for hydrogen storage in complex metal hydrides

    NASA Astrophysics Data System (ADS)

    Chopra, Irinder Singh

    The storage of hydrogen into metals in the form of complex metal hydrides is one of the most promising methods. However, the incorporation and release of hydrogen requires very high temperatures. The discovery that the addition of Ti compounds lowers NaAlH4 decomposition barriers closer to ambient conditions, has re-ignited the field, and it is believed that surface processes are responsible for H2 dissociation and mass transport required to form the hydrogenated materials. Such surface reactions mechanisms are however difficult to study with typical spectroscopic and imaging surface science tools. Alanes lack contrast under electron microscopes and can modify the Scanning Tunneling Microscopy (STM) tips. Infrared spectroscopy would be a sensitive probe to investigate the adsorption of hydrogen providing, but has so far failed to detect chemisorbed hydrogen on Ti-doped Al surfaces due to the weak Al-H dynamic dipole moment. Thus despite extensive investigations, the fundamental mechanisms of the role of Ti and alane formation have remained elusive. In this study combining surface infrared (IR) spectroscopy and density functional theory (DFT), we provide atomistic details about the role of Ti as a catalyst for hydrogen uptake and alane formation and evolution on single crystal Al(111) and Al(100) surfaces. We are able to detect H indirectly by using CO as a probe molecule of the weak Al-H species. We demonstrate that aluminum doped with very small amounts of titanium (in a specific configuration) can activate molecular hydrogen at temperatures as low as 90K. Once dissociated, hydrogen spills over from these catalytic sites on to the Al surface and protects the surface from further reactions. We also show that, on Ti-doped Al surfaces, the diffusion dynamics are severely altered by Ti doping (Atomic hydrogen and AlH3 are trapped at the Ti sites) as indicated by a marked decrease of higher alane concentrations, which is deleterious for hydrogen storage for which mass

  8. Effects of humic acid-metal complexes on hepatic carnitine palmitoyltransferase, carnitine acetyltransferase and catalase activities

    SciTech Connect

    Fungjou Lu; Youngshin Chen . Dept. of Biochemistry); Tienshang Huang . Dept. of Medicine)

    1994-03-01

    A significant increase in activities of hepatic carnitine palmitoyltransferase and carnitine acetyltransferase was observed in male Balb/c mice intraperitoneally injected for 40 d with 0.125 mg/0.1 ml/d humic acid-metal complexes. Among these complexes, the humic acid-As complex was relatively effective, whereas humic acid-25 metal complex was more effective, and humic acid-26 metal complex was most effective. However, humic acid or metal mixtures, or metal such as As alone, was not effective. Humic acid-metal complexes also significantly decreased hepatic catalase activity. A marked decrease of 60-kDa polypeptide in liver cytoplasm was also observed on SDS-polyacrylamide gel electrophoresis after the mice had been injected with the complexes. Morphological analysis of a histopathological biopsy of such treated mice revealed several changes in hepatocytes, including focal necrosis and cell infiltration, mild fatty changes, reactive nuclei, and hypertrophy. Humic acid-metal complexes affect activities of metabolic enzymes of fatty acids, and this results in accumulation of hydrogen peroxide and increase of the lipid peroxidation. The products of lipid peroxidation may be responsible for liver damage and possible carcinogenesis. Previous studies in this laboratory had shown that humic acid-metal complex altered the coagulation system and that humic acid, per se, caused vasculopathy. Therefore, humic acid-metal complexes may be main causal factors of not only so-called blackfoot disease, but also the liver cancer prevailing on the southwestern coast of Taiwan.

  9. Synthesis and Characterization of Transition Metal complexes with pyrimidine based ligand derivative

    NASA Astrophysics Data System (ADS)

    Awate, Ruchita; Mishra, Ashutosh; Mansuri, A.

    2016-10-01

    The article deals with a study of Synthesis Transition Metal Complexes Like copper and iron with Pyrimidine based ligand derivatives. The synthesized complex were characterized by XRD, SEM, FTIR. Mossbauer Spectra of Iron complex has also taken out to find oxidation state of iron after complexation.The aim of this study is to preparation and characterization with Transition Metal complexes by different physical and chemical characterization techniques.

  10. A palladium(II) complex containing both carbonyl and imine oxime ligands: Crystal structure, experimental and theoretical UV-vis, IR and NMR studies

    NASA Astrophysics Data System (ADS)

    Kaya, Yunus; Icsel, Ceyda; Yilmaz, Veysel T.; Buyukgungor, Orhan

    2013-05-01

    A new palladium(II) complex, [Pd(ppeieo)(inap)]·DMSO (ppeieo = (1E,2E)-phenyl-[(1-phenylethyl)imino]-ethanal oxime and inap = isonitrosoacetophenone) has been synthesized and characterized by elemental analysis, UV-vis, IR, NMR. X-ray diffraction analysis of the DMSO solvate of the complex shows that the palladium(II) ion is coordinated in a distorted square-planar geometry by ppeieo and inap, which is formed during the hydrolysis of ppeieo. DFT (B3LYP/LANL2DZ) calculations on the complex have been carried out to correlate geometry and spectroscopic properties such as electronic, vibrational and NMR chemical shifts. The complete vibrational frequency assignments were made and the calculation results were applied to simulate infrared spectra of the title compound which shows good agreement with observed spectra. The calculated HOMO and LUMO energies show that several transitions including the π → π* and charge transfer occur within the molecule. The chemical shifts reasonably correspond to the calculated spectra.

  11. A palladium(II) complex containing both carbonyl and imine oxime ligands: crystal structure, experimental and theoretical UV-vis, IR and NMR studies.

    PubMed

    Kaya, Yunus; Icsel, Ceyda; Yilmaz, Veysel T; Buyukgungor, Orhan

    2013-05-01

    A new palladium(II) complex, [Pd(ppeieo)(inap)]·DMSO (ppeieo=(1E,2E)-phenyl-[(1-phenylethyl)imino]-ethanal oxime and inap=isonitrosoacetophenone) has been synthesized and characterized by elemental analysis, UV-vis, IR, NMR. X-ray diffraction analysis of the DMSO solvate of the complex shows that the palladium(II) ion is coordinated in a distorted square-planar geometry by ppeieo and inap, which is formed during the hydrolysis of ppeieo. DFT (B3LYP/LANL2DZ) calculations on the complex have been carried out to correlate geometry and spectroscopic properties such as electronic, vibrational and NMR chemical shifts. The complete vibrational frequency assignments were made and the calculation results were applied to simulate infrared spectra of the title compound which shows good agreement with observed spectra. The calculated HOMO and LUMO energies show that several transitions including the π→π(*) and charge transfer occur within the molecule. The chemical shifts reasonably correspond to the calculated spectra.

  12. Co-transport of metal complexes by the green mussel Perna viridis.

    PubMed

    Chuang, Chia-Ying; Wang, Wen-Xiong

    2006-07-15

    We examined the uptake of ligand-bound metals (Cd and Zn) by the green mussel Perna viridis using defined artificial seawater. Different free ion concentrations (1 pM to 10 microM) in uptake solutions were created by adding different amounts of total metals (Cd 0.1 nM to 0.1 mM; Zn 0.5 nM to 0.05 mM) and ligands (EDTA, NTA, citric acid). Our results showed that Cd and Zn uptake could not be fully explained by the free Cd and Zn concentrations in the presence of different ligands, indicating that metal-ligand complexes were at least partially available for uptake by the mussels. Total Zn concentrations appeared to be a better predictor of metal uptake than the free Zn ion concentrations in the presence of different ligands. Uptake of lipophilic organic metal complexes was substantially greater than the hydrophilic metal complexes, even though the free ion concentration was comparable or lower. Moreover, the radiolabeled ligand compounds were directly accumulated by the mussels. The accumulation of metal complexes may explain the increased metal uptake with increasing ligand and total metal concentration, even though the free ion metal concentration was constant. Overall, our experimental results indicated that free metal ion cannot fully explain metal uptake since metal complex species were also available to the mussels to some extent, apparently through a co-transport process.

  13. Frustrated Lewis Pair-Like Reactivity of Rare-Earth Metal Complexes: 1,4-Addition Reactions and Polymerizations of Conjugated Polar Alkenes.

    PubMed

    Xu, Pengfei; Yao, Yingming; Xu, Xin

    2017-01-26

    Three rare-earth aryloxide ion pairs {[L1REOAr](+) /[B(C6 F5 )4 ](-) ; L1=CH3 C(2,6-iPr2 C6 H3 N)CHC(CH3 )(NCH2 CH2 PPh2 ); RE=Sc, Y, Lu; Ar=2,6-tBu2 C6 H3 } were reported that feature rare-earth/phosphorus (RE/P) combinations exhibiting frustrated Lewis pair (FLP)-like 1,4-addition reactions towards conjugated carbonyl substrates (e.g., enone, ynone, and acrylic substrates). Furthermore, these RE/P complexes were found to be effective catalysts for the polymerization of conjugated polar alkene monomers. Mechanistic studies revealed that the rare-earth metal-catalyzed polymerizations were initiated by new FLP-type 1,4-additions rather than traditional and ubiquitous covalent RE-E (E=H, C, N, etc.) bond insertion or single-electron transfer.

  14. Metal complex-based electron-transfer mediators in dye-sensitized solar cells

    DOEpatents

    Elliott, C. Michael; Sapp, Shawn A.; Bignozzi, Carlo Alberto; Contado, Cristiano; Caramori, Stefano

    2006-03-28

    This present invention provides a metal-ligand complex and methods for using and preparing the same. In particular, the metal-ligand complex of the present invention is of the formula: L.sub.a-M-X.sub.b where L, M, X, a, and b are those define herein. The metal-ligand complexes of the present invention are useful in a variety of applications including as electron-transfer mediators in dye-sensitized solar cells and related photoelectrochromic devices.

  15. Water-in-Supercritical CO2 Microemulsion Stabilized by a Metal Complex.

    PubMed

    Luo, Tian; Zhang, Jianling; Tan, Xiuniang; Liu, Chengcheng; Wu, Tianbin; Li, Wei; Sang, Xinxin; Han, Buxing; Li, Zhihong; Mo, Guang; Xing, Xueqing; Wu, Zhonghua

    2016-10-17

    Herein we propose for the first time the utilization of a metal complex for forming water-in-supercritical CO2 (scCO2 ) microemulsions. The water solubility in the metal-complex-stabilized microemulsion is significantly improved compared with the conventional water-in-scCO2 microemulsions stabilized by hydrocarbons. Such a microemulsion provides a promising route for the in situ CO2 reduction catalyzed by a metal complex at the water/scCO2 interface.

  16. Synthesis, characterization and biological relevance of some metal (II) complexes with oxygen, nitrogen and oxygen (ONO) donor Schiff base ligand derived from thiazole and 2-hydroxy-1-naphthaldehyde

    NASA Astrophysics Data System (ADS)

    Nagesh, G. Y.; Mruthyunjayaswamy, B. H. M.

    2015-04-01

    The novel Schiff base ligand 2-((2-hydroxynaphthalen-1-yl)methylene)-N-(4-phenylthiazol-2-yl)hydrazinecarboxamide (L) obtained by the condensation of N-(4-phenylthiazol-2-yl)hydrazinecarboxamide with 2-hydroxy-1-naphthaldehyde and its newly synthesized Cu(II), Co(II), Ni(II), Zn(II) and Cd(II) complexes have been characterized by microanalysis, molar conductance, IR, 1H NMR, ESI-mass, UV-Visible, TGA/DTA, ESR and powder X-ray diffraction data to explicate their structures. The IR results confirmed the tridentate binding of the ligand involving oxygen atom of amide carbonyl, azomethine nitrogen and naphthol oxygen. 1H NMR spectral data of the ligand (L) and its Zn(II) complex agreed well with the proposed structures. Thermogravimetric studies for Cu(II) and Ni(II) complexes indicated the presence of coordinated water molecules and the final product is the metal oxide. In order to appraise the effect of antimicrobial activity of metal ions upon chelation, the newly synthesized ligand and its metal complexes were screened for their antimicrobial activity by minimum inhibitory concentration (MIC) method. The DNA cleavage activities were studied using plasmid DNA pBR322 (Bangal re Genei, Bengaluru, Cat. No 105850) as a target molecule by agarose gel electrophoresis method. The brine shrimp bioassay was also carried out to study the in vitro cytotoxicity properties against Artemia salina. Furthermore, the antioxidant activity were determined in vitro by reduction of 1,1-diphenyl-2-picryl hydrazyl (DPPH). The ligand exhibited better in vitro-antioxidant activity than its metal complexes.

  17. Photogeneration of Very Active Homogeneous Catalysts Using Laser Light Excitation of Iron Carbonyl Precursors.

    DTIC Science & Technology

    1980-12-29

    Chem. Ser., 1978, 168, 189. 4. (a) Howard, J.F.; Chalk, A.J. " Organic Synthesis via Metal Carbonyls", Vol. 2, Wender, I.; Pino, P., eds., Wiley: New...and Identio’~ bo Ube& 6) laser chemistry, photocatalysis , metal carbonyls, hydrosilation, 0- isomerization 24. (Conin on s aide It ncoela nd Ident~ify...catalyst, could become the rate limiting feature. The results are given below. Photocatalysis experiments according to equations (1) and (2) were carried

  18. Chiral and nonchiral [OsX2(diphosphane)(diamine)] (X: Cl, OCH2CF3) complexes for fast hydrogenation of carbonyl compounds.

    PubMed

    Baratta, Walter; Barbato, Cinzia; Magnolia, Santo; Siega, Katia; Rigo, Pierluigi

    2010-03-08

    The osmium complexes trans-[OsCl(2)(dppf)(diamine)] (dppf: 1,1'-bis(diphenylphosphino)ferrocene; diamine: ethylenediamine in 3, propylenediamine in 4) were prepared by the reaction of [OsCl(2)(PPh(3))(3)] (1) with the ferrocenyl diphosphane, dppf and the corresponding diamine in dichloromethane. The reaction of derivative 3 with NaOCH(2)CF(3) in toluene afforded the alkoxide cis-[Os(OCH(2)CF(3))(2)(dppf)(ethylenediamine)] (5). The novel precursor [Os(2)Cl(4)(P(m-tolyl)(3))(5)] (2) allows the synthesis of the chiral complexes trans-[OsCl(2)(diphosphane)(1,2-diamine)] (6-9; diphosphane: (R)-[6,6'-dimethoxy(1,1'-biphenyl)-2,2'-diyl]bis[1,1-bis(3,5-dimethylphenyl)phosphane] (xylMeObiphep) or (R)-(1,1'-binaphthalene)-2,2'-diylbis[1,1-bis(3,5-dimethylphenyl)phosphane] (xylbinap); diamine=(R,R)-1,2-diphenylethylenediamine (dpen) or (R,R)-1,2-diaminocyclohexane (dach)), obtained by the treatment of 2 with the diphosphane and the 1,2-diamine in toluene at reflux temperature. Compounds 3-5 in ethanol and in the presence of NaOEt catalyze the reduction of methyl aryl, dialkyl, and diaryl ketones and aldehydes with H(2) at low pressure (5 atm), with substrate/catalyst (S/C) ratios of 10,000-200,000 and achieving turnover frequencies (TOFs) of up to 3.0 x 10(5) h(-1) at 70 degrees C. By employment of the chiral compounds 6-9, different ketones, including alkyl aryl, bulky tert-butyl, and cyclic ketones, have successfully been hydrogenated with enantioselectivities up to 99% and with S/C ratios of 5000-100,000 and TOFs of up to 4.1 x 10(4) h(-1) at 60 degrees C.

  19. Carbonylations of alkenes with CO surrogates.

    PubMed

    Wu, Lipeng; Liu, Qiang; Jackstell, Ralf; Beller, Matthias

    2014-06-16

    Alkene carbonylation reactions are important for the production of value-added bulk and fine chemicals. Nowadays, all industrial carbonylation processes make use of highly toxic and flammable carbon monoxide. In fact, these properties impede the wider use of carbonylation reactions in industry and academia. Hence, performing carbonylations without the use of CO is highly desired and will contribute to the further advancement of sustainable chemistry. Although the use of carbon monoxide surrogates in alkene carbonylation reactions has been reported intermittently in the last 30 years, only recently has this area attracted significant interest. This Minireview summarizes carbonylation reactions of alkenes using different carbon monoxide surrogates.

  20. Immobilizing Molecular Metal Dithiolene-Diamine Complexes on 2D Metal-Organic Frameworks for Electrocatalytic H2 Production.

    PubMed

    Dong, Renhao; Zheng, Zhikun; Tranca, Diana C; Zhang, Jian; Chandrasekhar, Naisa; Liu, Shaohua; Zhuang, Xiaodong; Seifert, Gotthard; Feng, Xinliang

    2017-02-16

    Carbon electrocatalysts consisting of metal complexes such as MNx or MSx are promising alternatives to high-cost Pt catalysts for the hydrogen evolution reaction (HER). However, the exact HER active sites remain elusive. Here, molecular metal dithiolene-diamine (MS2 N2 , M=Co and Ni), metal bis(dithiolene) (MS4 ), and metal bis(diamine) (MN4 ) complexes were selectively incorporated into carbon-rich 2D metal-organic frameworks (2D MOFs) as model carbon electrocatalysts. The 2D MOF single layers, powders, and composites with graphene were thus prepared and showed definite active sites for H2 generation. The electrocatalytic HER activity of the 2D MOF-based catalysts with different metal complexes follow the order of MS2 N2 >MN4 >MS4 . Moreover, the protonation preferentially occurred on the metal atoms, and the concomitant heterolytic elimination of H2 was favored on the M-N units in the MS2 N2 active centers. The results provide an in-depth understanding of the catalytic active sites, thus making way for the future development of metal complexes in carbon-rich electrode materials for energy generation.

  1. Thin films of metal oxides grown by chemical vapor deposition from volatile transition metal and lanthanide metal complexes

    NASA Astrophysics Data System (ADS)

    Pollard, Kimberly Dona

    1998-08-01

    This thesis describes the synthesis and characterization of novel volatile metal-organic complexes for the chemical vapor deposition (CVD) of metal oxides. Monomeric tantalum complexes, lbrack Ta(OEt)sb4(beta-diketonate)) are prepared by the acid-base reaction of lbrack Tasb2(OEt)sb{10}rbrack with a beta-diketone, (RC(O)CHsb2C(O)Rsp' for R = CHsb3, Rsp' = CFsb3; R = Rsp'=C(CHsb3)sb3; R = Csb3Fsb7,\\ Rsp'=C(CHsb3)sb3;\\ R=Rsp'=CFsb3; and R = Rsp' = CHsb3). The products are characterized spectroscopically. Thermal CVD using these complexes as precursors gave good quality Tasb2Osb5 thin films which are characterized by XPS, SEM, electrical measurements, and XRD. Factors affecting the film deposition such as the type of carrier gas and the temperature of the substrate were considered. Catalyst-enhanced CVD reactions with each of the precursors and a palladium catalyst, ((2-methylallyl)Pd(acac)), were studied as a lower temperature route to good quality Tasb2Osb5 films. The decomposition mechanism at the hot substrate surface was studied. Precursors for the formation of yttria by CVD were examined. New complexes of the form (Y(hfac)sb3(glyme)), (hfac = \\{CFsb3C(O)CHC(O)CFsb3\\}sp-,\\ glyme=CHsb3O(CHsb2CHsb2O)sb{n}CHsb3 for n = 1-4) were synthesized and characterized spectroscopically. X-ray structural determinations of three new complexes were obtained. CVD reaction conditions were determined which give YOF films and, with catalyst-enhanced CVD, reaction conditions which give selective formation of Ysb2Osb3, YOF, or YFsb3. The films were studied by XPS, SEM, and XRD. Decomposition mechanisms which lead to film formation, together with a possible route for fluorine atom transfer from the ligand to the metal resulting in fluorine incorporation, were studied by analysis of exhaust products using GC-MS. Novel precursors of the form lbrack Ce(hfac)sb3(glyme)rbrack,\\ (hfac=\\{CFsb3C(O)CHC(O)CFsb3\\}sp-,\\ glyme=CHsb3O(CHsb2CHsb2O)sb{n}CHsb3, n = 1-4) for CVD of ceria were

  2. From metallic gold to [Au(NHC)2](+) complexes: an easy, one-pot method.

    PubMed

    Lozada-Rodríguez, Leticia; Pelayo-Vázquez, José B; Rangel-Salas, Irma I; Alvarado-Rodríguez, José G; Peregrina-Lucano, A Aarón; Pérez-Centeno, Armando; López-Dellamary-Toral, Fernando A; Cortes-Llamas, Sara A

    2017-03-21

    A simple and direct method is described to prepare cationic bis(NHC)-Au(i) complexes containing N-alkyl or N-aryl NHC ligands to generate relevant gold complexes using metallic gold as the starting material.

  3. Membrane permeable luminescent metal complexes for cellular imaging

    NASA Astrophysics Data System (ADS)

    Neugebauer, Ute; Cosgrave, Lynda; Pellegrin, Yann; Devocelle, Marc; Forster, Robert J.; Keyes, Tia E.

    2012-06-01

    The spectroscopic and photophysical properties of ruthenium polypyridyl polypeptide conjugates of the type [Ru(bpy)2PIC-Argn]n+2+, where bpy is 2,2-bipyridyl (bpy), PIC is 2-(4-carboxyphenyl)imidazo[4,5- f][1,10]phenanthroline and PIC-Argn is this ligand peptide bonded to polyarginine where n is 5 or 8, is described. The resonance Raman spectroscopy of the peptide conjugated complex and parent are strongly pH dependent and demonstrate a switch of lowest energy charge transfer transition between bpy and pic ligands as s function of pH. The pKa of the imidazole ring on the complex is obtained from resonance Raman spectroscopy as 7.8 +/- 0.2. The luminescence lifetime of the complex is strongly oxygen dependent and a Stern-Volmer plot of O2 quenching for [Ru(bpy)2(PIC-Arg8)]10+ yielded a KSV value of 2300 +/- 420 M-1 which was independent of pH over the range 2 to 11. The complexes, because of their large Stokes shifts can, uniquely, be used under identical conditions of probe concentration and excitation wavelength for resonance Raman and luminescence cellular imaging. Cellular imaging was conducted using SP2 myeloma cells which confirmed that the [Ru(bpy)2(PIC-Arg8)]10+ is readily taken up by mammalian cells although the parent and pentarginine analogues are not membrane permeable. Preliminary examples of multi-parameter imaging using these probes were presented. Resonance Raman maps of [Ru(bpy)2(PIC-Arg8)]10+ within living myeloma cells showed on the basis of spectral discrimination, attributed to pH, three distinct regions of the cell could be identified, ascribed to the nucleus, the cytoplasm and the membranes. Luminescence lifetime imaging showed quite large variations in the probe lifetime within the living cell which was tentatively ascribed to variation in O2 concentration about the cell. Preliminary estimates of O2 concentration were made and it was found that the membranes, both inner and outer are the most O2 rich regions of the cell. Overall, we propose

  4. X-ray absorption spectroscopy of ground and excited rhenium-carbonyl-diimine complexes: evidence for a two-center electron transfer.

    PubMed

    El Nahhas, A; van der Veen, R M; Penfold, T J; Pham, V T; Lima, F A; Abela, R; Blanco-Rodriguez, A M; Záliš, S; Vlček, A; Tavernelli, I; Rothlisberger, U; Milne, C J; Chergui, M

    2013-01-17

    Steady-state and picosecond time-resolved X-ray absorption spectroscopy is used to study the ground and lowest triplet states of [ReX(CO)(3)(bpy)](n+), X = Etpy (n = 1), Cl, or Br (n = 0). We demonstrate that the transient spectra at both the Re L(3)- and Br K-edges show the emergence of a pre-edge feature, absent in the ground-state spectrum, which is associated with the electron hole created in the highest occupied molecular orbital following photoexcitation. Importantly, these features have the same dynamics, confirming previous predictions that the low-lying excited states of these complexes involve a two-center charge transfer from both the Re and the ligand, X. We also demonstrate that the DFT optimized ground and excited structures allow us to reproduce the experimental XANES and EXAFS spectra. The ground-state structural refinement shows that the Br atom contributes very little to the latter, whereas the Re-C-O scattering paths are dominant due to the so-called focusing effect. For the excited-state spectrum, the Re-X bond undergoes one of the largest changes but still remains a weak contribution to the photoinduced changes of the EXAFS spectrum.

  5. Capillary electrophoresis application in metal speciation and complexation characterization

    USDA-ARS?s Scientific Manuscript database

    Capillary electrophoresis is amenable to the separation of metal ionic species and the characterization of metal-ligand interactions. This book chapter reviews and discusses three representative case studies in applications of CE technology in speciation and reactions of metal with organic molecules...

  6. Copper(II) complexes with peptides based on the second cell binding site of fibronectin: metal coordination and ligand exchange kinetics.

    PubMed

    Pizzanelli, Silvia; Forte, Claudia; Pinzino, Calogero; Magrì, Antonio; La Mendola, Diego

    2016-02-07

    Copper(ii) complexes with short peptides based on the second cell binding site of fibronectin, PHSFN and PHSEN, have been characterized by potentiometric, UV-vis, CD, EPR and NMR spectroscopic methods. The histidine imidazole nitrogen is the anchoring site for the metal ion binding. Thermodynamic and spectroscopic evidence is given that the side chain oxygen donor atom of glutamyl residue in Ac-PHSEN-NH2 is also involved in the binding up to physiological pH. To determine ligand exchange kinetic parameters after the imidazole nitrogen anchoring, proton relaxation enhancement NMR data have been collected for the two hydrogen atoms of the imidazole ring in the temperature range 293-315 K at pH 5.2 and globally treated within different kinetic models for ligand exchange. The best fitting model involves two steps. In the first one, which is slow, a water molecule disengages a carbonyl or a carboxylate group coordinated to the metal ion in the complex formed by PHSFN or PHSEN, respectively. This stage is one order of magnitude slower for PHSEN, due to entropic effects. In the second step, which is fast, the complex just formed exchanges with the ligand. In this step, no appreciable differences are found for the two cases examined.

  7. Thermal properties of metal-metal bonded Pd(I) complexes supported onto porous Vycor glass.

    PubMed

    Gimenez, Iara F; Alves, Oswaldo L

    2008-06-01

    Thermal behavior of the complexes Pd2(dppm)2Cl2, Pd2(dppm)2(SnCl3)Cl and Pd2(dppm)2(SnCl3)2 (dppm=bis[diphenylphosphino(methane)], ((C6H5)2PCH2P(C6H5)2) in the solid state and immobilized onto porous Vycor glass was studied. Similar decomposition mechanisms were observed for the solid and immobilized complexes, with a small thermal stabilization upon immobilization. The decomposition products were characterized by X-ray diffractometry, Raman and diffuse reflectance infrared spectroscopy, which indicated the presence of a mixture of metallic palladium and oxidized species such as PdO,condensed phosphates, SnO2 and SnP2O7. According to X-ray diffractometry, the decomposition products of the immobilized complexes presented higher amounts of PdO than the solid-state residues, probably as an effect of interactions with silanol groups present in the glass surface.

  8. Structure and dynamics of solvent shells around photoexcited metal complexes.

    PubMed

    Szymczak, Jaroslaw J; Hofmann, Franziska D; Meuwly, Markus

    2013-05-07

    Understanding the geometry, energetics and dynamics of solvated transition metal (TM) compounds is decisive in characterizing and optimizing their function. Here, we demonstrate that it is possible to quantify the structural dynamics of solvated [Ru(II)(bpy)3], an important TM-complex for solar-energy harvesting research, by using state-of-the art force fields together with molecular simulations. Electronic excitation to [Ru(III)(bpy)3] leads to a nonequilibrium system in which excess energy is redistributed to the surrounding solvent following a cascade of dynamical effects that can be characterized by the simulations. The study reveals that the structure of the surrounding solvent relaxes towards the equilibrium on a sub-picosecond to a few-picosecond time scale. Analysis of solvent residence and rotational reorientation times during relaxation demonstrates increased dynamics in the inner solvation sphere on the picosecond time scale. Energy transfer to the solvent occurs on different time scales for the different degrees of freedom which range from a few hundred fs to several picoseconds.

  9. Superconductors and Complex Transition Metal Oxides for Tunable THz Plasmonic Metamaterials

    SciTech Connect

    Singh, Ranjan; Xiong, Jie; Azad, Md A.; Yang, Hao; Trugman, Stuart A.; Jia, Quanxi; Taylor, Antoinette; Chen, Houtong

    2012-07-13

    The outline of this presentation are: (1) Motivation - Non-tunability of metal metamaterials; (2) Superconductors for temperature tunable metamaterials; (3) Ultrafast optical switching in superconductor metamaterials; (4) Controlling the conductivity with infrared pump beam; (5) Complex metal oxides as active substrates - Strontium Titanate; and (6) Conclusion. Conclusions are: (1) High Tc superconductors good for tunable and ultrafast metamaterials; (2) Large frequency and amplitude tunability in ultrathin superconductor films; (3) Such tunable properties cannot be accessed using metals; (4) Complex metal oxides can be used as active substrates - large tunability; (5) Complex oxides fail to address the issue of radiation losses in THz metamaterials.

  10. Studies on Oligomer Metal Complexes Derived from Bisamic Acid of Pyromellitic Dianhydride and 4-Bromoaniline

    PubMed Central

    Patel, Yogesh S.

    2014-01-01

    Novel oligomer metal complexes (2a–f) of the ligand 2,5-bis((4-bromophenyl)carbamoyl) terephthalic acid (1) were prepared using transition metal salts and characterized by various spectroscopic techniques. The geometry of oligomer metal complexes was carried out by electronic spectral analysis and magnetic measurement studies. Polymeric properties have also been carried out. Ligand was synthesized using pyromellitic dianhydride and 4-bromoaniline. It was duly characterized. All novel synthesized compounds 1 and 2a–f were evaluated for their antibacterial and antifungal activity. The results showed significantly higher antibacterial and antifungal activity of oligomer metal complexes compared to the ligand. PMID:27379295

  11. Studies on Oligomer Metal Complexes Derived from Bisamic Acid of Pyromellitic Dianhydride and 4-Bromoaniline.

    PubMed

    Patel, Yogesh S

    2014-01-01

    Novel oligomer metal complexes (2a-f) of the ligand 2,5-bis((4-bromophenyl)carbamoyl) terephthalic acid (1) were prepared using transition metal salts and characterized by various spectroscopic techniques. The geometry of oligomer metal complexes was carried out by electronic spectral analysis and magnetic measurement studies. Polymeric properties have also been carried out. Ligand was synthesized using pyromellitic dianhydride and 4-bromoaniline. It was duly characterized. All novel synthesized compounds 1 and 2a-f were evaluated for their antibacterial and antifungal activity. The results showed significantly higher antibacterial and antifungal activity of oligomer metal complexes compared to the ligand.

  12. Solid State Pathways to Complex Shape Evolution and Tunable Porosity during Metallic Crystal Growth

    PubMed Central

    Valenzuela, Carlos Díaz; Carriedo, Gabino A.; Valenzuela, María L.; Zúñiga, Luis; O'Dwyer, Colm

    2013-01-01

    Growing complex metallic crystals, supported high index facet nanocrystal composites and tunable porosity metals, and exploiting factors that influence shape and morphology is crucial in many exciting developments in chemistry, catalysis, biotechnology and nanoscience. Assembly, organization and ordered crystallization of nanostructures into complex shapes requires understanding of the building blocks and their association, and this relationship can define the many physical properties of crystals and their assemblies. Understanding crystal evolution pathways is required for controlled deposition onto surfaces. Here, complex metallic crystals on the nano- and microscale, carbon supported nanoparticles, and spinodal porous noble metals with defined inter-feature distances in 3D, are accomplished in the solid-state for Au, Ag, Pd, and Re. Bottom-up growth and positioning is possible through competitive coarsening of mobile nanoparticles and their site-specific crystallization in a nucleation-dewetted matrix. Shape evolution, density and growth mechanism of complex metallic crystals and porous metals can be imaged during growth. PMID:24026532

  13. Protein carbonylation, cellular dysfunction, and disease progression

    PubMed Central

    Dalle-Donne, Isabella; Aldini, Giancarlo; Carini, Marina; Colombo, Roberto; Rossi, Ranieri; Milzani, Aldo

    2006-01-01

    Carbonylation of proteins is an irreversible oxidative damage, often leading to a loss of protein function, which is considered a widespread indicator of severe oxidative damage and disease-derived protein dysfunction. Whereas moderately carbonylated proteins are degraded by the proteasomal system, heavily carbonylated proteins tend to form high-molecular-weight aggregates that are resistant to degradation and accumulate as damaged or unfolded proteins. Such aggregates of carbonylated proteins can inhibit proteasome activity. A large number of neurodegenerative diseases are directly associated with the accumulation of proteolysis-resistant aggregates of carbonylated proteins in tissues. Identification of specific carbonylated protein(s) functionally impaired and development of selective carbonyl blockers should lead to the definitive assessment of the causative, correlative or consequential role of protein carbonylation in disease onset and/or progression, possibly providing new therapeutic aproaches. PMID:16796807

  14. Ab initio molecular orbital study of substituent effects in vaska type complexes (trans-IrL{sub 2}(CO)X): Electron affinities, ionization potentials, carbonyl stretch frequencies, and the thermodynamics of H{sub 2} dissociative addition

    SciTech Connect

    Abu-Hasanayn, F.; Goldman, A.S.; Krogh-Jespersen, K.

    1994-10-26

    Ab initio electronic structure calculations are used to study substituent effects in Vaska-type complexes, trans-IrL{sub 2}(CO)X (1-X) (X = F, Cl, Br, I, CN, H, CH{sub 3}, SiH{sub 3}, OH, and SH; L = PH{sub 3}). Both the electron affinity and the ionization potential of 1-X are computed to increase upon descending the halogen series of complexes, which indicates, surprisingly, that the complexes with more electronegative halogens are more difficult to reduce and easier to oxidize. The computed electron affinity trend is consistent with the half-wave reduction potential trend known for 1-X (L = PPh{sub 3}; X = F, Cl, Br, and I). Computed carbonyl stretch frequencies for 1-X are greater than experimental values (L = PPh{sub 3}), but observed trends are well reproduced. The redox and spectroscopic trends are discussed in terms of the substituent effects on the electronic structure of 1-X, particularly as revealed in the molecular orbital energy level diagrams of these complexes. The reaction energy for H{sub 2} addition to 1-X, leading to the cis,trans-(H){sub 2}IrL{sub 2}(CO)X (2-X) product, has been computed. After electron correlation effects are included (MP4(SDTQ)), the reaction enthalpy computed for 1-CI is {minus}18.4 kcal/mol (L = PH{sub 3}) as compared to a reported experimental value of {minus}14 kcal/mol (L = PPh{sub 3}). Compared with available experimental data, the electronic effects of L(L = PH{sub 3}, NH{sub 3}, or AsH{sub 3}) and X on the thermodynamics of the H{sub 2} addition reaction are accurately reproduced by the model calculations at all levels of theory (HF and MPn). Formation of the hypothetical products cis,trans- and trans,trans-(H){sub 2}IrL{sub 2}(CO)X(2-X and 3-X) (X = BH{sub 2}, NH{sub 2}, and PH{sub 2}) is used to demonstrate that {pi}-acceptor substituents promote the H{sub 2} addition reaction to 1-X while {pi}-donor substituents disfavor addition.

  15. Novel Route to Transition Metal Isothiocyanate Complexes Using Metal Powders and Thiourea

    NASA Technical Reports Server (NTRS)

    Harris, Jerry D.; Eckles, William E.; Hepp, Aloysius F.; Duraj, Stan A.; Hehemann, David G.; Fanwick, Phillip E.; Richardson, John

    2003-01-01

    A new synthetic route to isothiocyanate-containing materials is presented. Eight isothiocyanate- 4-methylpyridine (y-picoline) compounds were prepared by refluxing metal powders (Mn, Fe, Co, Ni, and Cu) with thiourea in y-picoline. With the exception of compound 5,prepared with Co, the isothiocyanate ligand was generated in situ by the isomerization of thiourea to NH4+SCN- at reflux temperatures. The complexes were characterized by x-ray crystallography. Compounds 1,2, and 8 are the first isothiocyanate- 4-methylpyridine anionic compounds ever prepared and structurally characterized. Compounds 1 and 2 are isostructural with four equatorially bound isothiocyanate ligands and two axially bound y-picoline molecules. Compound 8 is a five-coordinate copper(II) molecule with a distorted square-pyramidal geometry. Coordinated picoline and two isothiocyanates form the basal plane and the remaining isothiocyanate is bound at the apex. Structural data are presented for all compounds.

  16. Phosphorylation of C-H bonds of aromatic compounds using metals and metal complexes

    NASA Astrophysics Data System (ADS)

    Budnikova, Yu H.; Sinyashin, O. G.

    2015-09-01

    Key achievements and current trends in the development of methods for phosphorylation of aromatic C-H bonds catalyzed by metal salts and complexes are considered. The most important and promising approaches of the last decade, including those concerning the synthesis and properties of arylphosphonates, are distinguished. Methods for the introduction of a phosphonate group into non-activated and functionally substituted aromatic compounds and heteroaromatic molecules and phosphorylation-cyclization reactions involving acetylenes, 2-isocyanobiphenyls and alkynoates are analyzed. The possibilities of ligand-directed phosphorylation of compounds with aromatic C-H bonds and presumed mechanisms and intermediates in the C-P bond formation reactions are considered. The potential of this extensively developing research trend in organic and organoelement chemistry is highlighted. The bibliography includes 263 references.

  17. Characterization of oxide supported metal carbonyl clusters

    NASA Astrophysics Data System (ADS)

    Evans, John

    The chemisorption of [Ma 3(CO) 1 2] on silica (M = Ru and Os) and alumina (M = Os) has been studied by vibrational and X-ray absorption spectroscopies making close comparisons with model compounds. The results indicate that the first chemisorption species observed has the form [M 3H(CO) 10(O---O)]; the bridging hydride was observed directly for the silica systems as evidenced by the M-H-M bending vibration in the i.r. Also consistent with this structure are the EXAFS analysis of the Ru/SiOz material. This indicated an essentially equilateral ruthenium triangle and coordination to oxygen. The published low frequency Raman data on the Os/Al2Oa product was shown to match most closely with that of model compounds with a bidentate oxygen donor ligand (acac or O2CR). The tethered cluster [O s3H 2(CO) 9(PPh 2C 2H 4SIL)] was found to be a relatively short lived species on a silica surface. Under ambient conditions it reacts further and the i.r., EXAFS and 31P NMR data of this species suggest that the two osmium atoms not coordinated to the tethering phosphine become involved with a bidentate site from the surface.

  18. Complex transition metal hydrides: linear correlation of countercation electronegativity versus T-D bond lengths.

    PubMed

    Humphries, T D; Sheppard, D A; Buckley, C E

    2015-06-30

    For homoleptic 18-electron complex hydrides, an inverse linear correlation has been established between the T-deuterium bond length (T = Fe, Co, Ni) and the average electronegativity of the metal countercations. This relationship can be further employed towards aiding structural solutions and predicting physical properties of novel complex transition metal hydrides.

  19. Assigning Oxidation States to Some Metal Dioxygen Complexes of Biological Interest.

    ERIC Educational Resources Information Center

    Summerville, David A.; And Others

    1979-01-01

    The bonding of dioxygen in metal-dioxygen complexes is discussed, paying particular attention to the problems encountered in assigning conventional oxidation numbers to both the metal center and coordinated dioxygen. Complexes of iron, cobalt, chromium, and manganese are considered. (BB)

  20. 40 CFR 721.4680 - Metal salts of complex inorganic oxyacids (generic name).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Metal salts of complex inorganic... AGENCY (CONTINUED) TOXIC SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.4680 Metal salts of complex inorganic...

  1. Assigning Oxidation States to Some Metal Dioxygen Complexes of Biological Interest.

    ERIC Educational Resources Information Center

    Summerville, David A.; And Others

    1979-01-01

    The bonding of dioxygen in metal-dioxygen complexes is discussed, paying particular attention to the problems encountered in assigning conventional oxidation numbers to both the metal center and coordinated dioxygen. Complexes of iron, cobalt, chromium, and manganese are considered. (BB)

  2. Infrared Spectroscopic Analysis of Linkage Isomerism in Metal-Thiocyanate Complexes

    ERIC Educational Resources Information Center

    Baer, Carl; Pike, Jay

    2010-01-01

    We developed an experiment suitable for an advanced inorganic chemistry laboratory that utilizes a cooperative learning environment, which allows students to develop an empirical method of determining the bonding mode of a series of unknown metal-thiocyanate complexes. Students synthesize the metal-thiocyanate complexes and obtain the FT-IR…

  3. Site-selective hydrolysis of tRNA by lanthanide metal complexes

    SciTech Connect

    Hayashi, Nobuhiro ); Takeda, Naoya; Yashiro, Morio; Watanabe, Kimitsuna; Komiyama, Makoto ); Shiiba, Tetsuro )

    1993-12-22

    tRNA[sup Phe] is site-selectively hydrolyzed by lanthanide metal complexes (Ce(III), Eu(III), La(III)) of hexaimine macrocyclic ligands. The selectivities of the complexes are much higher than those of the metal ions and are strongly dependent on the ligand structure. The tertiary structure of tRNA is essential for the site-selective scission.

  4. Infrared Spectroscopic Analysis of Linkage Isomerism in Metal-Thiocyanate Complexes

    ERIC Educational Resources Information Center

    Baer, Carl; Pike, Jay

    2010-01-01

    We developed an experiment suitable for an advanced inorganic chemistry laboratory that utilizes a cooperative learning environment, which allows students to develop an empirical method of determining the bonding mode of a series of unknown metal-thiocyanate complexes. Students synthesize the metal-thiocyanate complexes and obtain the FT-IR…

  5. Testing the nature of reaction coordinate describing interaction of H2 with carbonyl carbon, activated by Lewis acid complexation, and the Lewis basic solvent: A Born-Oppenheimer molecular dynamics study with explicit solvent

    NASA Astrophysics Data System (ADS)

    Heshmat, Mojgan; Privalov, Timofei

    2017-09-01

    Using Born-Oppenheimer molecular dynamics (BOMD), we explore the nature of interactions between H2 and the activated carbonyl carbon, C(carbonyl), of the acetone-B(C6F5)3 adduct surrounded by an explicit solvent (1,4-dioxane). BOMD simulations at finite (non-zero) temperature with an explicit solvent produced long-lasting instances of significant vibrational perturbation of the H—H bond and H2-polarization at C(carbonyl). As far as the characteristics of H2 are concerned, the dynamical transient state approximates the transition-state of the heterolytic H2-cleavage. The culprit is the concerted interactions of H2 with C(carbonyl) and a number of Lewis basic solvent molecules—i.e., the concerted C(carbonyl)⋯H2⋯solvent interactions. On one hand, the results presented herein complement the mechanistic insight gained from our recent transition-state calculations, reported separately from this article. But on the other hand, we now indicate that an idea of the sufficiency of just one simple reaction coordinate in solution-phase reactions can be too simplistic and misleading. This article goes in the footsteps of the rapidly strengthening approach of investigating molecular interactions in large molecular systems via "computational experimentation" employing, primarily, ab initio molecular dynamics describing reactants-interaction without constraints of the preordained reaction coordinate and/or foreknowledge of the sampling order parameters.

  6. Testing the nature of reaction coordinate describing interaction of H2 with carbonyl carbon, activated by Lewis acid complexation, and the Lewis basic solvent: A Born-Oppenheimer molecular dynamics study with explicit solvent.

    PubMed

    Heshmat, Mojgan; Privalov, Timofei

    2017-09-07

    Using Born-Oppenheimer molecular dynamics (BOMD), we explore the nature of interactions between H2 and the activated carbonyl carbon, C(carbonyl), of the acetone-B(C6F5)3 adduct surrounded by an explicit solvent (1,4-dioxane). BOMD simulations at finite (non-zero) temperature with an explicit solvent produced long-lasting instances of significant vibrational perturbation of the H-H bond and H2-polarization at C(carbonyl). As far as the characteristics of H2 are concerned, the dynamical transient state approximates the transition-state of the heterolytic H2-cleavage. The culprit is the concerted interactions of H2 with C(carbonyl) and a number of Lewis basic solvent molecules-i.e., the concerted C(carbonyl)⋯H2⋯solvent interactions. On one hand, the results presented herein complement the mechanistic insight gained from our recent transition-state calculations, reported separately from this article. But on the other hand, we now indicate that an idea of the sufficiency of just one simple reaction coordinate in solution-phase reactions can be too simplistic and misleading. This article goes in the footsteps of the rapidly strengthening approach of investigating molecular interactions in large molecular systems via "computational experimentation" employing, primarily, ab initio molecular dynamics describing reactants-interaction without constraints of the preordained reaction coordinate and/or foreknowledge of the sampling order parameters.

  7. Heterobimetallic coordination polymers involving 3d metal complexes and heavier transition metals cyanometallates

    SciTech Connect

    Peresypkina, Eugenia V.; Samsonenko, Denis G.; Vostrikova, Kira E.

    2015-04-15

    The results of the first steps in the design of coordination polymers based on penta- and heptacyanometallates of heavier d transitions metals are presented. The 2D structure of the coordination polymers: [(Mn(acacen)){sub 2}Ru(NO)(CN){sub 5}]{sub n} and two complexes composed of different cyanorhenates, [Ni(cyclam)]{sub 2}[ReO(OH)(CN){sub 4}](ClO{sub 4}){sub 2}(H{sub 2}O){sub 1.25} and [Cu(cyclam)]{sub 2}[Re(CN){sub 7}](H{sub 2}O){sub 12}, was confirmed by single crystal XRD study, the rhenium oxidation state having been proved by the magnetic measurements. An amorphism of [M(cyclam)]{sub 3}[Re(CN){sub 7}]{sub 2} (M=Ni, Cu) polymers does not allow to define strictly their dimensionality and to model anisotropic magnetic behavior of the compounds. However, with high probability a honey-comb like layer structure could be expected for [M(cyclam)]{sub 3}[Re(CN){sub 7}]{sub 2} complexes, studied in this work, because such an arrangement is the most common among the bimetallic assemblies of hexa- and octacyanometallates with a ratio [M(cyclam)]/[M(CN){sub n}]=3/2. For the first time was prepared and fully characterized a precursor (n-Bu{sub 4}N){sub 2}[Ru(NO)(CN){sub 5}], soluble in organic media. - Graphical abstract: The very first results in the design of 2D coordination polymers based on penta- and heptacyanometallates of 4d and5d transitions metals are presented. - Highlights: • Design of coordination polymers based on penta- and heptacyanometallates. • New Ru and Re cyanide based heterobimetallic coordination complexes. • Hydrolysis and ox/red processes involving [Re(CN){sub 7}]{sup 3+} during crystallization. • High magnetic anisotropy of [M(cyclam)]{sub 3}[Re(CN){sub 7}]{sub 2}(H{sub 2}O){sub n}, M=Cu, Ni, complexes.

  8. Design of new metal complexes of 2-(3-amino-4,6-dimethyl-1H-pyrazolo[3,4-b]pyridin-1-yl)aceto-hydrazide: Synthesis, characterization, modelling and antioxidant activity

    NASA Astrophysics Data System (ADS)

    Abdel-Monem, Yasser K.; Abou El-Enein, Saeyda A.; El-Sheikh-Amer, Mona M.

    2017-01-01

    The entitled ligand and its metal complexes derived from chloride salts of Mn(II), Co(II), Ni(II), and Cu(II), and Cd(NO3)2 were prepared. The structures were confirmed by analytical, different spectral techniques and thermogravimetric analysis. Complexes are formed with stoichiometries 1:1 and 2:3 (M:L) with electrolytic nature, except Cd(II) complex is nonelectrolyte. All complexes have octahedral geometry, except Cu(II) complex has square planar structure. IR spectra established that ligand coordinates with metal ions through nitrogen and oxygen atoms of amino and carbonyl groups of hydrazide moiety in neutral form. The mechanism of thermal decomposition of complexes was discussed. The antioxidant activity of compounds was proved, where Cu(II) complex displays higher antioxidant activity than that of other complexes. Molecular modeling and docking of the investigated complexes into hAChE was reported based on Molsoft ICM 3.4-8C program and the complexes improved the activity of ligand.

  9. Reactivity of silicon carbonyl with ethylene

    NASA Astrophysics Data System (ADS)

    Belanzoni, P.; Giorgi, G.; Cerofolini, G. F.

    2006-02-01

    The reaction of silicon atom with carbonyl has recently been investigated by density functional calculations. A few relatively stable silicon carbonyl compounds have been found. In this Letter, the reactivity of silicon tetracarbonyl with ethylene has been investigated by a density functional approach. The calculations predict this carbonylation procedure as an alternative to the use of highly toxic phosgene commonly required in addition reactions of carbonyl to unsaturated compounds.

  10. Essentially Molecular Metal Complexes Anchored to Zeolite: Synthesis and Characterization of Rhodium Complexes and Ruthenium Complexes Prepared from Rh(acac)(2-C2H4)2 and cis-Ru(acac)2( -C2H4)2

    SciTech Connect

    Ogino, I.; Gates, B

    2010-01-01

    Mononuclear complexes of rhodium and of ruthenium, Rh(acac)({eta}{sup 2}-C{sub 2}H{sub 4}){sub 2} and cis-Ru(acac)2({eta}{sup 2}-C{sub 2}H{sub 4}){sub 2} (acac = C{sub 5}H{sub 7}O{sub 2}{sup -}), were used as precursors to synthesize metal complexes bonded to zeolite {beta}. Infrared (IR) and extended X-ray absorption fine structure (EXAFS) spectra show that the species formed from Rh(acac)({eta}{sup 2}-C{sub 2}H{sub 4}){sub 2} was Rh({eta}{sup 2}-C{sub 2}H{sub 4}){sub 2}{sup +}, which was bonded to the zeolite at aluminum sites via two Rh-O bonds. Reaction of this supported rhodium complex with CO gave the supported rhodium gem-dicarbonyl Rh(CO){sub 2}{sup +}, which was characterized by two {nu}{sub CO} bands in the IR spectrum, at 2048 and 2115 cm{sup -1}, that were sharp (fwhm of 2115-cm{sup -1} band = 5 cm{sup -1}), indicating a high degree of uniformity of the supported species. Nearly the same result was observed (Liang, A. et al. J. Am. Chem. Soc. 2009, 131, 8460) for the isostructural rhodium complex supported on dealuminated HY zeolite, which was characterized by frequencies of the {nu}{sub CO} bands that were 4 and 2 cm{sup -1}, respectively, greater than those characterizing the zeolite {beta}-supported complex. This comparison indicates that the Rh atoms in Rh({eta}{sup 2}-C{sub 2}H{sub 4}){sub 2}{sup +} anchored on zeolite {beta} were slightly more electron-rich than those on zeolite Y. This inference is supported by EXAFS results showing shorter Rh-C bonds in the zeolite {beta}-supported rhodium ethene complex than in the zeolite Y-supported rhodium ethene complex. In contrast to these supported rhodium complexes, the zeolite {beta}-supported ruthenium samples were shown by IR and EXAFS spectroscopies to consist of mixtures of mononuclear ruthenium complexes with various numbers of acac ligands; when CO reacted with the supported ruthenium complexes, the resultant ruthenium carbonyls were characterized by {nu}{sub CO} spectra characteristic of both

  11. Removal of heavy metals by sulfide precipitation in the presence of complexing agents

    SciTech Connect

    Ku, Y.

    1986-01-01

    Heavy metal removals and particle size distributions were presented for both hydroxide precipitation and sulfide precipitation of zinc, cadmium, copper, and nickel in the presence of various complexing agents. Both batch and continuous experiments were performed for synthetic and actual metal-containing wastewaters. Metal concentrations complexing agent concentrations, sulfide dosages, pH levels of the solutions, and reaction or residence times were varied to determine the reaction kinetics. Sulfide precipitation always achieved lower residual metal concentrations than the corresponding hydroxide precipitation. The presence of strong complexing agents severely inhibited the removal of heavy metal by the precipitation process. Weak complexing agents exhibited little effect on the chemical equilibria for both hydroxide and sulfide precipitation systems. Weak complexing agents did affect the particle size distribution through a nucleation/growth inhibition, general forming smaller particles.

  12. Preparation, Physicochemical Characterization and Biological Evaluation of some Hesperidin Metal Complexes

    PubMed Central

    Daoud, Safa; Afifi, Fatma U; Al-Bakri, Amal G; Kasabri, Violet; Hamdan, Imad I

    2014-01-01

    The ability of hesperidin (HP) to form complexes with five metals; cobalt, nickel, zinc, calcium and magnesium was investigated. The complexation was studied using U.V spectroscopic titration, in methanol as well as aqueous buffer solutions (physiological conditions). Potential complexes were studied by IR and NMR spectroscopy, melting point and their solubility were also evaluated. The interaction of HP and its metal complexes with DNA was investigated by U.V spectroscopy. HP and its potential complexes were also tested for their ability to inhibit alpha amylase and alpha glucosidase enzymes. The results indicated that HP can form 1:1 complexes with cobalt, nickel and zinc in methanolic solution but not in aqueous buffers. Both HP and its metal complexes were found to intercalate DNA, at physiological condition, with preference to GC rich sequences. HP-metal complexes appeared to have higher affinity towards poly A DNA than the free HP. Neither HP nor its complexes exhibited antimicrobial activity against Staphylococcus aureus, Escherichia coli, Pseudomonas aeruginosa or Candida albicans. Results showed that HP has little inhibitory action on glucosidase and amylase enzymes with no obvious effect of complexation on the behavior of free HP. In conclusion HP was shown to form 1:complexes with the studied metal in methanol but not in aqueous buffer solutions. In presence of DNA however, complex formation in aqueous solutions seem to be encouraged with differential effect between the complexes and free HP. PMID:25276191

  13. Transition Metal d-Orbital Splitting Diagrams: An Updated Educational Resource for Square Planar Transition Metal Complexes

    ERIC Educational Resources Information Center

    Bo¨rgel, Jonas; Campbell, Michael G.; Ritter, Tobias

    2016-01-01

    The presentation of d-orbital splitting diagrams for square planar transition metal complexes in textbooks and educational materials is often inconsistent and therefore confusing for students. Here we provide a concise summary of the key features of orbital splitting diagrams for square planar complexes, which we propose may be used as an updated…

  14. Transition Metal d-Orbital Splitting Diagrams: An Updated Educational Resource for Square Planar Transition Metal Complexes

    ERIC Educational Resources Information Center

    Bo¨rgel, Jonas; Campbell, Michael G.; Ritter, Tobias

    2016-01-01

    The presentation of d-orbital splitting diagrams for square planar transition metal complexes in textbooks and educational materials is often inconsistent and therefore confusing for students. Here we provide a concise summary of the key features of orbital splitting diagrams for square planar complexes, which we propose may be used as an updated…

  15. Production of metal particles and clusters

    NASA Technical Reports Server (NTRS)

    Mcmanus, S. P.

    1982-01-01

    The feasibility of producing novel metals or metal clusters in a low gravity environment was studied. The production of coordinately unsaturated metal carbonyls by thermolysis or photolysis of stable metal carbonyls has the potential to generate novel catalysts by this technique. Laser irradiation of available metal carbonyls was investigated. It is found that laser induced decomposition of metal carbonyls is feasible for producing a variety of coordinately unsaturated species. Formation of clustered species does occur but is hampered by weak metal-metal bonds.

  16. Electronic interactions in metal complexed photoconducting polymers : a ZINDO study.

    SciTech Connect

    Manas, E. S.; Chen, L. X.; Chemistry; Univ. of Pennsylvania School of Medicine

    2000-12-01

    Semi-empirical (INDO/s) calculations have been conducted on molecular fragments with zero to three phenylenevinylene (PV) units attached to 4 and 4{prime} positions of a 2,2{prime}-bipyridine (bpy) group, with and without chelated metal ions, mimicking metal-free and metal-chelated photoconducting polymers 1 and 2 [Chen et al., J. Phys. Chem. B 104 (2000) 1950]. The calculations suggest that: (1) a global lowering of the molecular orbital energy levels due to metal-chelation is responsible for the observed red-shift in the lowest energy transitions; and (2) metal chelation attenuates {pi}-electron delocalization. The relevance of these effects to photoluminescence of metal-chelated polymers is also discussed.

  17. Rhenium(I) Carbonyl Complexes of 2,4,6-Tris(2-pyridyl)-1,3,5-triazine (TPT). Rhenium(I)-Promoted Methoxylation of the Triazine Ring Carbon Atom in Dinuclear Rhenium Complexes

    PubMed Central

    Chen, Xiaoyuan; Femia, Frank J.; Babich, John W.; Zubieta, Jon A.

    2010-01-01

    2,4,6-Tris(2-pyridyl)-1,3,5-triazine (TPT) bridged dinuclear rhenium(I) tricarbonyl halide complexes with the composition (μ-TPT)[ReX(CO)3]2 (3, X = Cl; 4, X = Br) can be made either by one-pot reaction of TPT with 2 equiv of [ReX(CO)5] (X = Cl and Br) in chloroform or by reacting mononuclear [ReX(CO)3(TPT)] 2 (1, X = Cl; 2, X = Br) with an excess amount of [ReX(CO)5]. Crystal data are as follows. 1: monoclinic, P21/c, a = 11.751(1) Å, b = 11.376(1) Å, c = 15.562(2) Å, β = 103.584(2)°, V = 2022.0(4) Å3, Z = 4. 2: monoclinic, P21/c, a = 11.896(1) Å, b = 11.396(1) Å, c = 15.655(1) Å, β = 104.474(2)°, V = 2054.9(3) Å3, Z = 4. 3: triclinic, P1‒, a = 11.541(2) Å, b = 12.119(2) Å, c = 13.199(2) Å, α = 80.377(2)°, β = 76.204(3)°, γ = 66.826-(2)°, V = 1642.5(4) Å3, Z ) 2. Crystals of 4 crystallized from acetone: triclinic, P1‒, a = 11.586(5) Å, b = 12.144(5) Å, c = 13.364(6) Å, α = 80.599(7)°, β = 76.271(8)°, γ = 67.158(8)°, V = 1678.0(12) Å3, Z = 2. Crystals of 4′ are obtained from CH2Cl2–pentane solution: monoclinic, C2/c, a = 17.555(4) Å, b = 15.277(3) Å, c = 13.093(3) Å, β = 111.179(3)°, V = 3274.0(12) Å3, Z = 4. By contrast, similar reactions in the presence of methanol yielded complexes with the composition [μ-C3N3(OMe)(py)2(pyH)][ReX(CO)3]2 (5, X = Cl; 6, X = Br). Crystal data for 5: monoclinic, C2/c, a = 26.952(2) Å, b = 16.602(1) Å, c = 14.641(1) Å, β = 116.147(1)°, V = 5880.5(8) Å3, Z = 8. 6: monoclinic, C2/c, a = 27.513(3) Å, b = 16.740(2) Å, c = 14.837(2) Å, β = 116.925(2)°, V = 6092.8(10) Å3, Z = 8. An unusual metal-induced methoxylation at the carbon atom of the triazine ring of the bridging TPT ligand was observed. The nucleophilic attack of MeO− on C(3) results in a tetrahedral geometry around the carbon atom. Concomitantly, the uncoordinated pyridyl ring is protonated and rotated into a perpendicular orientation relative to the central C3N3 ring. Reaction of TPT with [NEt4]2[ReBr3-(CO)3] in

  18. [Studies on the interaction of the metal complex of hydrazide of podophyllic acid with DNA].

    PubMed

    Wang, Ping-Hong; Zhang, Qi; Wang, Liu-Fang; Song, Yu-Min; Qu, Jian-Qiang; Liu, Ying-Qian

    2006-05-01

    The interaction between the metal complex of hydrazide of podophyllic acid and calf thymus (CT) DNA was studied by using absorption spectra, fluorescence spectra and DNA heat denaturation. It was found that the intensity of the maximal absorption peaks from absorption spectra is weakened in the presence of the metal complex of hydrazide of podophyllic acid compared with that in the absence of the metal complex. All the experimental results show that the intercalation mode was proved to exist between HDPP-Ni complexes and CT DNA.

  19. Tetracyclines metal complexation: Significance and fate of mutual existence in the environment.

    PubMed

    Pulicharla, Rama; Hegde, Krishnamoorthy; Brar, Satinder Kaur; Surampalli, Rao Y

    2017-02-01

    Concern over tetracyclines (TCs) complexation with metals in the environment is growing as a new class of emerging contaminants. TCs exist as a different net charged species depending on their dissociation constants, pH and the surrounding environment. One of the key concerns about TCs is its strong tendency to interact with various metal ions and form metal complexes. Moreover, co-existence of TCs and metals in the environment and their interactions has shown increased antibiotic resistance. Despite extensive research on TCs complexation, investigations on their antibiotic efficiency and pharmacological profile in bacteria have been limited. In addition, the current knowledge on TCs metal complexation, their fate and risk assessment in the environment are inadequate to obtain a clear understanding of their consequences on living systems. This indicates that vital and comprehensive studies on TCs-metal complexation, especially towards growing antibiotic resistance trends are required. This review summarizes the role of TCs metal complexation on the development of antibiotic resistance. Furthermore, impact of metal complexation on degradation, toxicity and the fate of TCs in the environment are discussed and future recommendations have been made.

  20. Cationization of organometallo carbonyl compounds by fast ion bombardment

    NASA Astrophysics Data System (ADS)

    Siuzdak, Gary; Wendeborn, Sebastian V.; Nicolaou, K. C.

    1992-01-01

    Organodicobalt, organochromium, and organomolybdenum carbonyl complexes have been studied using fast ion bombardment mass spectrometry. It has been found that the addition of cesium iodide to the liquid matrix, m-NBA, can significantly enhance the ability to observed the precursor ions of these organometallics through charge localization. In most cases the [M + Cs]+ ions were more abundant than the radical cations M-, the protonated molecules [M + H]+, or the sodium cationized molecules [M + Na]+ which were either unobservable or less intense than those treated with the cesium iodide salt solution. The decomposition of the compounds took place primarily through the successive loss of carbonyls from the radical cation with some carbonyl loss observed through the protonated and cationized species. The FAB matrix ions produced when cesium iodide was added to m-NBA also allowed for internal calibration.