Sample records for 2,4-pentanedione

  1. The chemical processing of gas-phase carbonyl compounds by sulfuric acid aerosols: 2,4-pentanedione

    NASA Astrophysics Data System (ADS)

    Nozière, Barbara; Riemer, Daniel D.

    This work investigates the interactions between gas-phase carbonyl compounds and sulfuric acid aerosols. It focuses on understanding the chemical processes, giving a first estimate of their importance in the atmosphere, and suggesting directions for further investigations. The solubility and reactivity of a compound with a large enolization constant, 2,4-pentanedione, in water/sulfuric acid solutions 0-96 wt% have been investigated at room temperature using the bubble column/GC-FID technique. 2,4-pentanedione was found to undergo aldol condensation at acidities as low as 20 wt% H 2SO 4, that is, well in the tropospheric range of aerosol composition. In agreement with well-established organic chemical knowledge, this reaction resulted in changes of color of the solutions of potential importance for the optical properties of the aerosols. 2,4-pentanedione was also found to undergo retroaldol reaction, specific to dicarbonyl compounds, producing acetone and acetaldehyde. The Henry's law coefficient for 2,4-pentanedione was found to be a factor 5 larger than the one of acetone over the whole range of acidity, with a value in water of H (297 K)=(155±27) M atm -1. A chemical system is proposed to describe the transformations of carbonyl compounds in sulfuric acid aerosols. Aldol condensation is likely to be the most common reaction for these compounds, probably involving a large number of the ones present in the atmosphere and a wide range of aerosol compositions. The enolization constant contributes as a proportional factor to the rate constant for aldol condensation, and is shown in this work to contribute as an additive constant to the Henry's law coefficient. In addition to the many important aspects of these reactions illustrated in this work, the rate of aldol condensation was estimated to be potentially fast enough for the losses of some compounds in acidic aerosols to compete with their gas-phase chemistry in the atmosphere.

  2. Systemic toxicity from repeated cutaneous contact with 2,4-pentanedione.


    Ballantyne, B


    2,4-Pentanedione (2,4 PD; CAS Number 123-54-6) is an industrial chemical with potential for skin contact. Repeated exposure studies by peroral and inhalation routes have shown central neurotoxicity and possible effects on the immune system. To determine the likelihood for systemic toxicity by cutaneous contact with 2,4-PD, a short-term repeated skin contact study was conducted in New Zealand white rabbits. The planned protocol was for dosing, with 0.5, 1.0 and 1.5 ml undiluted 2,4-PD by 6 h occlusive contact/d for 9 d; these were equivalent to dosages of 244, 975 and 1463 mg/kg/d. A dosage-related skin irritation was seen macroscopically and by light microscopy, which was minimal at the low dosage. Mortalities occurred at the mid (1/6 males, 3/6 females) and high dosages (5/12 males, 7/12 females), with deaths between the 2nd and 5th dosing day. In view of these mortalities and signs, dosing of the mid and high dose animals was discontinued, and survivors were kept to the end of the dosing period. Signs at the mid and high dosage included hypoactivity, tremors, convulsions, uncoordinated movements and prostration, and appeared between the 2nd and 4th dose. Body weight gain and food consumption were reduced for the mid and high dosage groups. Increased hemoglobin, hematocrit and erythrocyte counts may have been associated with dehydration, and increased heterophil count with cutaneous inflammation. Several serum biochemical changes reflected cutaneous irritation, and high creatine kinase activity was probably a consequence of convulsions. Immune effects included decreased lymphocyte counts and lymphoid necrosis in spleen and thymus. Central neuropathology in the mid and high dosages was seen as hemorrhages and neuronal degeneration, the latter principally in piriform cortex, globus pallidus and hippocampus. No peripheral neuropathy was present. 244 mg/kg/d was the no-effects dosage for systemic toxicity. This study confirmed a potential for systemic toxicity

  3. Vapor pressure and viscosity of 1,1,1,5,5,5-hexafluoro-2,4-pentanedione

    SciTech Connect

    George, M.A.; Young, K.M.; Robertson, E.A. III; Beck, S.E.; Voloshin, G.


    1,1,1,5,5,5-Hexafluoro-2,4-pentanedione (H{sup +}hfac) is a potential vapor-phase cleaning agent for removing trace transition metals from silicon wafer surfaces and for in situ removal of spurious bulk copper in Cu CVD chamber cleaning applications. The viscosity and vapor pressure of the reactive chelating ligand, H{sup +}hfac have been determined. The viscosity of liquid H{sup +}hfac was determined to be (1.39 {+-} 0.19) {times} 10{sup {minus}3} Pa{center_dot}s at 24 C and (8.35 {+-} 0.25) {times} 10{sup {minus}4} Pa{center_dot}s at 35 C. The vapor pressure of H{sup +}hfac was found to range from 4 kPa at 0 C to 49.5 kPa at 57 C. The viscosity was measured using a capillary tube viscometer, and the vapor pressure was measured using a mass transfer gas saturation apparatus. These methods were employed because conventional methodologies would have produced unreliable data due to the formation of the tetrol hydrate of H{sup +}hfac inside the apparatus and potentially exposed laboratory personnel to hazardous working conditions.

  4. Conformational studies of 3-aminomethylene-2,4-pentanedione using vibrational and NMR spectra, and ab initio calculations

    NASA Astrophysics Data System (ADS)

    Gróf, M.; Gatial, A.; Milata, V.; Prónayová, N.; Sümmchen, L.; Salzer, R.


    The IR, Raman and NMR spectra of 3-aminomethylene-2,4-pentanedione (AMP) H 2N sbnd CH dbnd C(COCH 3) 2 were measured. According to the NMR spectra in chloroform and more polar DMSO at room temperature, the sample exists as single entity. On the other hand vibrational spectra revealed that in less polar solutions AMP exists as two conformers with EZ or ZZ orientation of acetyl groups whereas in more polar solvent only one EZ conformer is observed. Such interpretation was confirmed also by the temperature-dependent measurements of IR spectra in chloroform. The observed IR and Raman bands were compared with harmonic vibrational frequencies, calculated using ab initio MP2 and B3LYP density functional methods in 6-31G ∗∗ basis set, and assigned on the basis of potential energy distribution. In addition, the geometries and relative energies of possible conformers of AMP were also evaluated at the same levels of theory and compared with the data from X-ray analysis which revealed that AMP exists in solid state as EZ conformer. The influence of environment polarity on this conformational equilibrium is discussed with respect to the SCRF solvent effect calculations using PCM, IPCM and ONSAGER models.

  5. Substituent Effects on Keto-Enol Equilibria Using NMR Spectroscopy

    ERIC Educational Resources Information Center

    Manbeck, Kimberly A.; Boaz, Nicholas C.; Bair, Nathaniel C.; Sanders, Allix M. S.; Marsh, Anderson L.


    In this extension to a classic physical chemistry experiment, students record the proton nuclear magnetic resonance spectra of the [beta]-diketones 2,4-pentanedione, 3-methyl-2,4-pentanedione, and 3-chloro-2,4-pentanedione to investigate the effect of substituents on keto-enol tautomerization equilibria. From the integrated intensities of keto and…

  6. Spectroscopic investigation of the structure of complex compounds of Cu(II), Co(II), and Ni(II) with. cap alpha. - and. beta. -diketone

    SciTech Connect

    Krymova, N.M.; Ivanov, V.E.; Ostapkevich, N.A.


    In the reactions of Cu(II), Co(II), and Ni(II) chlorides with 2,3-butanedione and 2,4-pentanedione isonicotinoylhydrazones in neutral and weakly acid media complex compounds of the addition-product type are formed, but in an alkaline medium inner-complex compounds are formed. By methods of electronic and ESR spectroscopy it was shown that the Cu(II) complex compounds have a planar-square structure, the Ni(II) complexes are octrahedral, but the Co(II) complexes have a tetrahedral or distorted tetrahedral structure. In the spectrochemical series 2,3-butanedione and 2,4-pentanedione isonicotinoylhydrazones occupy positions between water and ammonia.

  7. Studies on Some New Ru(III) Complexes Using aryl-azo Pentane- 2,4-dione and 2,6-bis (2'-Benzimidazolyl) Pyridine as Ligands: Synthesis, Spectroscopic, Luminescent, Electrochemical and Biological Activities

    PubMed Central

    Yadaw, Ajay K.; Phadke, Ratna S.; Choi, Chang S.; Araki, Koji


    Some ruthenium(III) complexes with aryl-azo 2,4-pentanedione as co-ligands (L1H - L3H2) have been synthesized and characterized spectroscopically IR, 1H NMR, UV/Vis, ESR, conductimetric) along with elemental analysis and FAB-mass data. Their luminescent and redox properties have been studied. The antibacterial, anti-HIV and antitmnour activities have also been reported. PMID:18475977

  8. Formation and stability of lanthanide complexes and their encapsulation into polymeric microspheres

    SciTech Connect

    Mumper, R.J.; Jay, M.


    The complexation of lanthanides (Ln) with dicarbonyl compounds (acetylacetone, acac; ethyl acetoacetate; 3-ethyl-2,4-pentanedione; 2,4-hexanedione; 3-methyl-2,4-pentanedione; and diethyl malonate) was investigated using a potentiometric titration technique. The ability of a dicarbonyl compound to complex with the lanthanide elements was greatly dependent on its pK{sub a} and on the pH of the titrated solution. Selected lanthanide complexes (Ln complexes) were incorporated into spherical poly(L-lactic acid)(PLA) matrices and irradiated in a nuclear reactor with neutrons to produce short-lived high-energy {Beta}-particle-emitting radioisotopes. The lanthanides investigated (Ho, Dy, Sm, and La) were chosen on the basis of their physical and nuclear properties. A transition element (Re) was also studied. The small decrease in the ionic radii of the lanthanides with increasing atomic number led to (a) greater ability to extract and complex from an aqueous solution with complexing agents, (b) larger formation and stability constants for the Ln complexes, (c) increased solubility of the Ln complexes in chloroform, and (d) increase in the maximum percent incorporation of the stable lanthanides in PLA spheres. Ho(aca) was found to be the most promising candidate of the complexes studied on the basis of the above observations and due to the favorable physical properties of {sup 165}Ho and nuclear properties of {sup 166}Ho. 21 refs., 5 figs., 4 tabs.

  9. Aldol Condensation of Volatile Carbonyl Compounds in Acidic Aerosols

    NASA Astrophysics Data System (ADS)

    Noziere, B.; Esteve, W.


    Reactions of volatile organic compounds in acidic aerosols have been shown recently to be potentially important for organic aerosol formation and growth. Aldol condensation, the acid-catalyzed polymerization of carbonyl compounds, is a likely candidate to enhance the flux of organic matter from the gas phase to the condensed phase in the atmosphere. Until now these reactions have only been characterized for conditions relevant to synthesis (high acidities and liquid phase systems) and remote from atmospheric ones. In this work, the uptake of gas-phase acetone and 2,4\\-pentanedione by sulfuric acid solutions has been measured at room temperature using a Rotated Wetted Wall Reactor coupled to a Mass Spectrometer. The aldol condensation rate constants for 2,4\\-pentanedione measured so far for sulfuric acid solutions between 96 and 70 % wt. display a variation with acidity in agreement with what predicted in the organic chemical literature. The values of these constants, however, are much lower than expected for this compound, and comparable to the ones of acetone. Experiments are underway to complete this study to lower acidities and understand the discrepancies with the predicted reactivity.

  10. High performance of inverted polymer solar cells with cobalt oxide as hole-transporting layer

    NASA Astrophysics Data System (ADS)

    Wang, Xiangdong; Peng, Qing; Zhu, Weiguo; Lei, Gangtie


    Cobalt oxide (II, III) (CoOx) was inserted as efficient hole-transporting interlayer between the active layer and top electrode in inverted polymer solar cells (PSCs) with titanium (diisopropoxide) bis(2, 4-pentanedionate) (TIPD) as an electron selective layer. The work function of CoOx was measured by Kelvin probe and the device performances with different thicknesses of cobalt oxide were studied. The device with CoOx exhibited a remarkable improvement in power conversion efficiency compared with that without CoOx, which indicated that CoOx efficiently prevented the recombination of charge carriers at the organic/top electrode interface. The performance improvement was attributed to the fact that the CoOx thin film can module the Schottky barrier and form an ohmic contact at the organic/metal interface, which makes it a promising hole-transporting layer.

  11. Performance improvement of polymer solar cells by using a solution processible titanium chelate as cathode buffer layer

    NASA Astrophysics Data System (ADS)

    Tan, Zhan'ao; Yang, Chunhe; Zhou, Erjun; Wang, Xiang; Li, Yongfang


    A solution processible titanium chelate, titanium (diisopropoxide) bis (2,4-pentanedionate) (TIPD), was used as the cathode buffer layer in the polymer solar cells (PSCs) based on the blend of poly[2-methoxy-5-(2'-ethylhexyloxy)-1,4-phenylenevinylene] and [6,6]-phenyl-C61-butyric acid methyl ester. Introducing TIPD buffer layer reduced the interface resistance between the active layer and Al electrode, leading to a lower device resistance. The power conversion efficiency of the PSC with TIPD buffer layer reached 2.52% under the illumination of AM1.5, 100mW/cm2, which is increased by 51.8% in comparison with that (1.66%) of the device without TIPD buffer layer under the same experimental conditions.

  12. Intramolecular hydrogen bonding and vibrational assignment of 1,1,1-trifluoro-5,5-dimethyl-2,4-hexanedione

    NASA Astrophysics Data System (ADS)

    Afzali, R.; Vakili, M.; Nekoei, A.-R.; Tayyari, S. F.


    Intramolecular hydrogen bonding (IHB) and vibrational frequencies of 1,1,1-trifluoro-5,5-dimethyl-2,4-hexanedione (TFDMHD) have been investigated by means of density functional theory (DFT) calculations, Atoms in Molecules (AIM) analysis, natural bond orbital (NBO) theory, and IR and Raman spectroscopies. The results are compared with those of 1,1,1-trifluoro-2,4-pentanedione (TFAA) and 5,5-dimethyl hexane-2,4-dione (DMHD). The hydrogen bonding energies (EHB) of the most stable chelated enol forms, obtained by AIM theory are in the range of 17.1-20.0 kcal/mol. The IR and Raman spectra of TFDMHD and its deuterated analog were clearly assigned. Comparing the calculated and experimental band frequencies and intensities suggests coexisting of three stable cis-enol forms in comparable proportions in the sample. The theoretical calculations and spectroscopic results indicate that the IHB strength of TFDMHD is between those of TFAA and DMHD.

  13. The imidazole role in strontium beta-diketonate complexes formation.


    Marchetti, Fabio; Pettinari, Claudio; Pettinari, Riccardo; Cingolani, Augusto; Gobetto, Roberto; Chierotti, Michele R; Drozdov, Andrei; Troyanov, Sergey I


    A selection of new strontium beta-diketonate derivatives (imH2)2[Sr2(beta-dike)6] [where imH = imidazole and beta-dike = tfac (tfacH = 1,1,1-trifluoro-2,4-pentanedione), tfbz (tfbzH = 1,1,1-trifluoro-4-phenyl-2,4-butanedione), or hfac (hfacH = 1,1,1,5,5,5-hexafluoro-2,4-pentanedione)], [Sr2(tfac)4(Meim)2(H2O)2], (MeimH)2[Sr(beta-dike)4] (where Meim = 1-methylimidazole and beta-dike = tfbz or hfac), [Sr2(thd)4(imH)2(EtOH)], and [Sr2(thd)4(Meim)2(EtOH)] (where thdH = 2,2,6,6-tetramethyl-3,5-heptanedione) have been synthesized and fully characterized. (imH2)2[Sr2(beta-dike)6] and (MeimH)2[Sr(beta-dike)4] are di- and mononuclear Sr anionic complexes, respectively, while [Sr2(tfac)4(Meim)2(H2O)2], [Sr2(thd)4(imH)2(EtOH)], and [Sr2(thd)4(Meim)2(EtOH)] are neutral dinuclear molecular derivatives. The derivative (imH2)2[Sr2(hfac)6] slowly decomposes in solution under aerobic conditions, giving (imH2)2[Sr(H2O)2(tfa)3](tfa) (tfaH = trifluoroacetic acid), which is an ionic compound containing polynuclear anionic chains composed of Sr(H2O)2(tfa)3 units. When a deficiency of imH is employed, the thdH proligand forms not only the dinuclear derivative [Sr2(thd)4(imH)2(EtOH)] but also an additional product with the formula [Sr(thd)2(H2O)2(EtOH)], in which the Sr atom is seven-coordinated. A complete solid-state characterization has been accomplished by comparing X-ray and solid-state 13C NMR data. Elucidation of the H-bond interaction between the heterocyclic rings and metal complexes by cross-polarization magic-angle-spinning 15N NMR is also reported. PMID:16562964

  14. Assessment of accidental intakes of uranyl acetylacetonate (UAA)

    SciTech Connect

    Fisher, D.R.; Briant, J.K.


    Uranyl acetylacetonate (UAA) is an organic complex of uranium used for military applications as a chemical catalyst in high explosives. It is prepared from depleted uranium metal (in lots of 5 kg to 7 kg) by dissolution in nitric acid, neutralization, and complexation with 2,4-pentanedione; the precipitate is dissolved in benzene and recrystallized, dried, ground, and packaged. About six workers at a small chemical company were exposed over a period of time to UAA powders during routine preparation and packaging of the uranium catalyst. The dissolution characteristics of the inhaled material were unknown and could not be determined from the published scientific literature. A 1.05-g sample of UAA powder was obtained from the responsible regulatory authority for further study to determine its chemical composition, and for dissolution in simulated lung fluid. We found the solubility of UAA to be equivalent to a mixture of 52% ICRP class D and 48% ICRP class W material. The annual limit on intake and the derived air concentration for radiological protection were estimated from this result for airborne exposure to UAA. A recycling biokinetic model was used to estimate both material-specific variations in urinary excretion rates and lung retention with time after accidental intakes. This study provides new information for evaluating future exposures to UAA.

  15. Efficient perovskite/fullerene planar heterojunction solar cells with enhanced charge extraction and suppressed charge recombination.


    Li, Cong; Wang, Fuzhi; Xu, Jia; Yao, Jianxi; Zhang, Bing; Zhang, Chunfeng; Xiao, Min; Dai, Songyuan; Li, Yongfang; Tan, Zhan'ao


    Alcohol soluble titanium chelate TIPD (titanium (diisopropoxide) bis(2,4-pentanedionate)) was used as an electron transporting layer to form an ohmic contact with the negative electrode, aiming to enhance the charge extraction and suppress the charge recombination for high performance CH3NH3PbI3/PCBM-based PHJ perovskite solar cells. The TIPD layer shows excellent suitability to CH3NH3PbI3 perovskite synthesized by different methods. For one-step synthesized CH3NH3PbI3, the power conversion efficiency (PCE) of the device with the TIPD buffer reaches 8.75%, with a nearly 33% increase in comparison with the device without the buffer layer (6.58%). For two-step synthesized CH3NH3PbI3, an open-circuit voltage (Voc) of 0.89 V, a short-circuit current density (Jsc) of 22.57 mA cm(-2), and a fill factor (FF) of 64.5%, corresponding to a PCE of 12.95% for the device with a TIPD buffer layer were achieved, which is among the best performances reported in the literature for CH3NH3PbI3/PCBM-based PHJ perovskite solar cells. PMID:25962479

  16. Crystal structure, photoluminescence and electroluminescence of three bluish green light-emitting iridium complexes.


    Xu, Qiu-Lei; Liang, Xiao; Jiang, Liang; Zhao, Yue; Zheng, You-Xuan


    Three bis-cyclometalated iridium complexes ((TPP)2Ir(acac), (TPP)2Ir(tpip) and (TPP)2Ir(pic)) with 2-(2-trifluoromethyl)pyrimidine-pyridine (TPP) as the main ligand, 2,4-pentanedionate (acac), tetraphenylimidodiphosphinate (tpip) and picolinate (pic) as the ancillary ligands, respectively, were prepared. Their photoluminescence and electrochemistry properties were investigated in detail, and (TPP)2Ir(tpip) was also examined by X-ray crystallography. These complexes show bluish green emission with a quantum efficiency of 11-14%. The organic light emitting diodes (OLEDs) with the structure of ITO/TAPC (1,1-bis[4-(di-p-tolylamino)phenyl]cyclohexane, 40 nm)/mCP (1,3-bis(9H-carbazol-9-yl)benzene, 10 nm)/Ir complex (8 wt%):PPO21 (3-(diphenylphosphoryl)-9-(4-(diphenylphosphoryl)phenyl)-9H-carbazole, 25 nm)/TmPyPB (1,3,5-tri(m-pyrid-3-yl-phenyl)benzene, 50 nm)/LiF (1 nm)/Al (100 nm) were fabricated to evaluate the potential application of these complexes. A (TPP)2Ir(tpip) emitter based device showed the best performance of a maximum current efficiency (ηc) value of 37.61 cd A(-1) and a maximum external quantum efficiency (EQE) of 13.7% with low efficiency roll-off. PMID:27030006

  17. Composition-dependent electrocatalytic activity of palladium-iridium binary alloy nanoparticles supported on the multiwalled carbon nanotubes for the electro-oxidation of formic acid.


    Bao, Jianming; Dou, Meiling; Liu, Haijing; Wang, Feng; Liu, Jingjun; Li, Zhilin; Ji, Jing


    Surface-functionalized multiwalled carbon nanotubes (MWCNTs) supported Pd100-xIrx binary alloy nanoparticles (Pd100-xIrx/MWCNT) with tunable Pd/Ir atomic ratios were synthesized by a thermolytic process at varied ratios of bis(acetylacetonate) palladium(II) and iridium(III) 2,4-pentanedionate precursors and then applied as the electrocatalyst for the formic acid electro-oxidation. The X-ray diffraction pattern (XRD) and transmission electron microscope (TEM) analysis showed that the Pd100-xIrx alloy nanoparticles with the average size of 6.2 nm were uniformly dispersed on the MWCNTs and exhibited a single solid solution phase with a face-centered cubic structure. The electrocatalytic properties were evaluated through the cyclic voltammetry and chronoamperometry tests, and the results indicated that both the activity and stability of Pd100-xIrx/MWCNT were strongly dependent on the Pd/Ir atomic ratios: the best electrocatalytic performance in terms of onset potential, current density, and stability against CO poisoning was obtained for the Pd79Ir21/MWCNT. Moreover, compared with pure Pd nanoparticles supported on MWCNTs (Pd/MWCNT), the Pd79Ir21/MWCNT exhibited enhanced steady-state current density and higher stability, as well as maintained excellent electrocatalytic activity in high concentrated formic acid solution, which was attributed to the bifunctional effect through alloying Pd with transition metal. PMID:26132867

  18. Noninnocently Behaving Bridging Anions of the Widely Distributed Antioxidant Ellagic Acid in Diruthenium Complexes.


    Mandal, Abhishek; Grupp, Anita; Schwederski, Brigitte; Kaim, Wolfgang; Lahiri, Goutam Kumar


    Dinuclear compounds [L2Ru(μ-E)RuL2](n) where L is acetylacetonate (acac(-), 2,4-pentanedionate), 2,2'-bipyridine (bpy), or 2-phenylazopyridine (pap) and EH4 is ellagic acid, an antioxidative bis-catechol natural product, were studied by voltammetric and spectroelectrochemical techniques (UV-vis-NIR and electron paramagnetic resonance (EPR)). The electronic structures of the isolated forms (NBu4)2[(acac)2Ru(μ-E)Ru(acac)2] ((NBu4)2[1]), [(bpy)2Ru(μ-E)Ru(bpy)2]ClO4 ([2]ClO4), and [(pap)2Ru(μ-E)Ru(pap)2] ([3]) were characterized by density functional theory (DFT) in conjunction with EPR and UV-vis-NIR measurements. The crystal structure of (NBu4)2[1] revealed the meso form and a largely planar Ru(μ-E)Ru center. Several additional charge states of the compounds were electrochemically accessible and were identified mostly as complexes with noninnocently behaving pap(0/•-) or bridging ellagate (E(n-)) anions (n = 2, 3, 4) but not as mixed-valence intermediates. The free anions E(n-), n = 1-4, were calculated by time-dependent DFT to reveal NIR transitions for the radical forms with n = 1 and 3 and a triplet ground state for the bis(o-semiquinone) dianion E(2-). PMID:26441246

  19. An iron(II) diketonate-diamine complex as precursor for thin film fabrication by atomic layer deposition

    NASA Astrophysics Data System (ADS)

    Bratvold, Jon E.; Carraro, Giorgio; Barreca, Davide; Nilsen, Ola


    A new divalent Fe precursor has been explored for deposition of iron-containing thin films by atomic layer deposition and molecular layer deposition (ALD/MLD). The Fe(II) β-diketonate-diamine complex, Fe(hfa)2TMEDA, (hfa = 1,1,1,5,5,5-hexafluoro-2,4-pentanedionate, TMEDA = N,N,N‧,N‧-tetramethylethylenediamine) can be handled in air, and sublimation at 60 °C ensures a satisfactory vaporization rate. The reactivity of the precursor does not allow for direct reaction with water as co-reactant. Nevertheless, it reacts with carboxylic acids, resulting in organic-inorganic hybrid materials, and with ozone, yielding α-Fe2O3. The divalent oxidation state of iron was maintained during deposition when oxalic acid was used as co-reactant, demonstrating the first preservation of Fe(II) from precursor to film during an MLD process. A self-saturating growth mode was proven by in situ quartz crystal microbalance (QCM) measurements, and the films were further characterized by grazing incidence X-ray diffraction (GIXRD), Fourier transform infrared spectroscopy (FTIR), and X-ray photoelectron spectroscopy (XPS).

  20. Improved determination of malonaldehyde by high-performance liquid chromatography with UV detection as 2,3-diaminonaphthalene derivative.


    Panseri, Sara; Chiesa, Luca Maria; Brizzolari, Andrea; Santaniello, Enzo; Passerò, Elena; Biondi, Pier Antonio


    A rapid, specific and simple procedure is proposed for the determination of free malonaldehyde (MA) contained in fish tissue. The method is the optimization of the reaction of MA with 2,3-diaminonaphthalene to afford a naphtodiazepinium ion that present a UV absorption at 311nm, useful for MA determination by HPLC with UV detection. The reaction proceeds in the presence of 25% acetonitrile at 37°C in 20min at pH 2 using 2,4-pentanedione as internal standard. The method has been applied to homogenized samples of canned mackerel fillets that were treated with 2,3-diaminonaphthalene in an acidic aqueous:acetonitrile mixture. The produced naphtodiazepinium ion was extracted in acetonitrile by a salting-out homogeneous liquid-liquid extraction. A standard calibration was carried out in the range 0.625-10nmol/g. The reliability of the procedure is demonstrated by linearity (r(2)=0.998), limit of detection (0.16nmol/g), limit of quantification (0.22nmol/g), repeatibility (RSD 5.57%), and intermediate precision (RSD 8.92%). PMID:25497496

  1. Photooxidation of water by NiTiO3 deposited from single source precursor [Ni2Ti2(OEt)2(micro-OEt)6(acac)4] by AACVD.


    Tahir, Asif Ali; Mazhar, Muhammad; Hamid, Mazhar; Wijayantha, K G Upul; Molloy, Kieran C


    A single-source heterobimetallic complex Ni2Ti2(OEt)2(mu-OEt)6(acac)4 (1) (acac=2,4-pentanedionate), having a low decomposition temperature and sufficient solubility in organic solvents, was synthesized by simple chemical techniques in high yield and analyzed by melting point, FTIR, single crystal X-ray analysis and thermal analysis. The TGA analysis proved that complex (1) underwent facile thermal decomposition at 500 degrees C to give NiTiO3 residue. In-house designed aerosol assisted chemical vapor deposition equipment was used to deposit high quality thin films of NiTiO3 on a SnO2 coated conducting glass substrate at 500 degrees C. An XRD analysis of the thin films proved the formation of crystalline NiTiO3 with average grain size 42 nm. Scanning electron microscopic studies (SEM) show that the thin films consist of flat, plate-like nanoparticles. The current-potential characteristics recorded under AM1.5 illumination indicate that NiTiO3 thin films are anodic and the photocurrent density at 1.23 V vs RHE (Reversible Hydrogen Electrode) is about 40 microA cm(-2). PMID:19417932

  2. Selected spectroscopic and magnetic properties of lanthanide complexes in polyimide XU-218

    NASA Technical Reports Server (NTRS)

    Stoakley, D. M.; Shillady, D. D.; Vallarino, L. M.; Gootee, W. A.; Smailes, D. L.


    Polyimide XU-218 films containing approximately 5 wt pct of Eu(III), Gd(III), Tb(III), and Er(III) were prepared, and the effects of complexing each of the metals with the following four ligands were investigated: N-phenylphthalamate (NPPA), 2,4-pentanedionate (AcAc), 1,3-diphenyl 1,3-propanedionate (DBM), and a new hexa-aza-macrocyclic (MAC) ligand. The tris-chelated complexes of the mononegative ligands NPPA, AcAc, and DBM produced transparent, flexible films, which had magnetic and spectral properties very similar to those of the parent lanthanide complexes, while complexes of MAC showed problems due to the presence of lattice water and yielded dark brittle films. AcAc caused little or no effect on the glass transition temperature (Tg), while NPPA and DBM complexes lowered Tg to 269-290 C, and MAC indicated moisture by inflexion at 95-100 C with a true Tg at 320 C. All lanthanide-containing films were paramagnetic.

  3. Efficient perovskite/fullerene planar heterojunction solar cells with enhanced charge extraction and suppressed charge recombination

    NASA Astrophysics Data System (ADS)

    Li, Cong; Wang, Fuzhi; Xu, Jia; Yao, Jianxi; Zhang, Bing; Zhang, Chunfeng; Xiao, Min; Dai, Songyuan; Li, Yongfang; Tan, Zhan'ao


    Alcohol soluble titanium chelate TIPD (titanium (diisopropoxide) bis(2,4-pentanedionate)) was used as an electron transporting layer to form an ohmic contact with the negative electrode, aiming to enhance the charge extraction and suppress the charge recombination for high performance CH3NH3PbI3/PCBM-based PHJ perovskite solar cells. The TIPD layer shows excellent suitability to CH3NH3PbI3 perovskite synthesized by different methods. For one-step synthesized CH3NH3PbI3, the power conversion efficiency (PCE) of the device with the TIPD buffer reaches 8.75%, with a nearly 33% increase in comparison with the device without the buffer layer (6.58%). For two-step synthesized CH3NH3PbI3, an open-circuit voltage (Voc) of 0.89 V, a short-circuit current density (Jsc) of 22.57 mA cm-2, and a fill factor (FF) of 64.5%, corresponding to a PCE of 12.95% for the device with a TIPD buffer layer were achieved, which is among the best performances reported in the literature for CH3NH3PbI3/PCBM-based PHJ perovskite solar cells.Alcohol soluble titanium chelate TIPD (titanium (diisopropoxide) bis(2,4-pentanedionate)) was used as an electron transporting layer to form an ohmic contact with the negative electrode, aiming to enhance the charge extraction and suppress the charge recombination for high performance CH3NH3PbI3/PCBM-based PHJ perovskite solar cells. The TIPD layer shows excellent suitability to CH3NH3PbI3 perovskite synthesized by different methods. For one-step synthesized CH3NH3PbI3, the power conversion efficiency (PCE) of the device with the TIPD buffer reaches 8.75%, with a nearly 33% increase in comparison with the device without the buffer layer (6.58%). For two-step synthesized CH3NH3PbI3, an open-circuit voltage (Voc) of 0.89 V, a short-circuit current density (Jsc) of 22.57 mA cm-2, and a fill factor (FF) of 64.5%, corresponding to a PCE of 12.95% for the device with a TIPD buffer layer were achieved, which is among the best performances reported in the literature

  4. Single-step fabrication of nanolamellar structured oxide ceramic coatings by metal-organic chemical vapor deposition.


    Eils, Nadine K; Mechnich, Peter; Keune, Hartmut; Wahl, Georg; Klages, Claus-Peter


    Oxide ceramic coatings in the system Y2O3-Al2O3-ZrO2 were fabricated in laboratory scale by using a MOCVD unit. A hot wall reactor was used along with different precursor feeding systems. Most experiments were carried out by using powder flash evaporation including a screw feeder for precursor powder delivery. For comparison, further samples were fabricated by using band flash evaporation and continuous evaporation from a crucible. Oxygen was used in all cases as reactant gas. Aluminium-tris-2,4-pentanedione (Al(acac)3), yttrium-tris-2,2,6,6-tetramethyl-3,5-heptanedione (Y(thd)3) and zirconium-tetrakis-2,2,6,6-tetramethyl-3,5-heptanedione (Zr(thd)4) were applied as metal-organic precursors because of their similar vaporization behaviour under the given conditions. The coating stoichiometry was varied from pure alumina to complex ternary compositions in the system Y2O3-Al2O3-ZrO2. Both kinds of ternary coatings fabricated by using flash evaporation methods show a nanolamellar microstructure in the as deposited state. Heat treating experiments at 1200 degrees C for up to 5 days enhance the lamellar character of the coating deposited by using powder flash evaporation. The lamellar microstructure is due to alternating YSZ enriched layers and YAG enriched layers in this state. However, the coating fabricated by using band flash evaporation shows a dense interpenetrating network of YSZ and YAG after heat treating instead of a lamellar microstructure observed in the as deposited state. PMID:22097592

  5. Synthesis and structures of tridentate ketoiminate zinc complexes bearing trifluoromethyl substituents that act as L-lactide ring opening polymerization initiators.


    Rezayee, Nomaan M; Gerling, Kimberly A; Rheingold, Arnold L; Fritsch, Joseph M


    A series of NNO ketoimines bearing trifluoromethyl substituents were synthesized from the Schiff base condensation of 1,3-diketones (1,1,1-trifluoro-5,5-dimethyl-2,4-hexanedione, 4,4,4-trifluoro-1-phenyl-1,3-butanedione, and 1,1,1-trifluoro-2,4-pentanedione, 1,1,1,5,5,5-hexafluoroacetylacetone) and 8-aminoquinoline or 8-amino-2-methylquinoline and isolated in 40-70% yield. The ketoimines were combined with zinc bis-(trimethylsilyl)amide to prepare a zinc amide complex in 41% yield or were combined with zinc bis-(trimethylsilyl)amide and 2,6-di-tert-butylphenol to prepare zinc phenoxide complexes in 81-94% yield. The ketoimines and zinc complexes were characterized with (1)H, (13)C, and (19)F NMR, absorbance spectroscopy, mass spectrometry, elemental analysis and X-ray crystallography. The mononuclear solid state structures of the zinc amide and phenoxide complexes showed tridentate coordination of the zinc center by the ketoiminate and monodentate coordination by the amide or phenoxide. The zinc complexes were assessed for their ability to catalyze the ring opening polymerization (ROP) of L-lactide into poly-lactic acid (PLA) with some complexes reaching 100% conversion in 3 h. As the monomer to catalyst ratio increased, the molecular weight of the isolated polymeric material increased in a nearly linear fashion while retaining a narrow molecular weight distribution. Homonuclear decoupled (1)H NMR spectra of the isolated polymeric material showed the retention of stereochemistry in the isotactic poly-L-lactic acid. Kinetic studies, where the substituents on the ketoiminate and quinolyl moiety were varied, showed that lower electron density on the Zn metal center yielded lower ROP catalytic activity than their electron rich counterparts. The complexes are proposed to use the coordination-insertion mechanism for living polymerization of L-lactide. PMID:23435405

  6. X-ray Emission Spectroscopy to Study Ligand Valence Orbitals in Mn Coordination Complexes

    SciTech Connect

    Smolentsev, Grigory; Soldatov, Alexander V; Messinger, Johannes; Merz, Kathrin; Weyhermuller, Thomas; Bergmann, Uwe; Pushkar, Yulia; Yano, Junko; Yachandra, Vittal K.; Glatzel, Pieter


    We discuss a spectroscopic method to determine the character of chemical bonding and for the identification of metal ligands in coordination and bioinorganic chemistry. It is based on the analysis of satellite lines in X-ray emission spectra that arise from transitions between valence orbitals and the metal ion 1s level (valence-to-core XES). The spectra, in connection with calculations based on density functional theory (DFT), provide information that is complementary to other spectroscopic techniques, in particular X-ray absorption (XANES and EXAFS). The spectral shape is sensitive to protonation of ligands and allows ligands, which differ only slightly in atomic number (e.g., C, N, O...), to be distinguished. A theoretical discussion of the main spectral features is presented in terms of molecular orbitals for a series of Mn model systems: [Mn(H2O)6]2+, [Mn(H2O)5OH]+, [Mn(H2O)5NH2]+, and [Mn(H2O)5NH3]2+. An application of the method, with comparison between theory and experiment, is presented for the solvated Mn2+ ion in water and three Mn coordination complexes, namely [LMn(acac)N3]BPh4, [LMn(B2O3Ph2)(ClO4)], and [LMn(acac)N]BPh4, where L represents 1,4,7-trimethyl-1,4,7-triazacyclononane, acac stands for the 2,4-pentanedionate anion, and B2O3Ph2 represents the 1,3-diphenyl-1,3-dibora-2-oxapropane-1,3-diolato dianion.

  7. Harvard--MIT research program in short-lived radiopharmaceuticals

    SciTech Connect

    Not Available


    This report describes progress on five projects. The first project showed a 1000 fold concentration of the cationic complex {sup 99m}Tc (MIBI) in heart cell mitochondria vs heart cell cytoplasm, as determined by high resolution electron probe microanalysis. Additional technetium-99m based complexes are being developed and tested. The second project involves evaluating technetium acetylacteonates as potential indicators of cerebral blood flow. An intermediate in the synthesis of a technetium porphyrin complex has been synthesized; an oxotechnetium(V)-2,4-pentanedione complex has been prepared and is currently being characterized. The third project involves using radio labelled antibodies for diagnosis and treatment of cancer. An early discovery was that chloramine-T based iodination protocols resulted in a reversal of the charge on mouse lgGs. Immunoperoxidase-labelled monoclonal antibody MOv 18 was shown to bind specifically to the most frequent ovarian aderon carcinomas, and not to healthy tissue, making this antibody a good candidate for immunotherapy or immunodetection. Work on a specific immunotherapy protocol suffered a setback when one reagent, a {sup 125}I-biotin complex, proved to be unstable in vivo. The fourth project involves labelling antibodies with positron emitting radionuclides. Radiofluorination was accomplished through reductive alkylation of {sup 18}F-aldehyde, or pentafluorophenyl esters. Radioiodination was accomplished using alkyl-tin derivation exchange. The fifth project examined antibody modification for use in radioimmune imaging. Technetium-99m-labelled lgG was shown to be biologically equivalent to Indium-III-labelled lgG for imaging focal sites of inflamation. Also, Indium III labelling of small bioactive peptides was examined as a means of imaging important physiological processes. 44 refs., 2 figs.

  8. Structure and NIR-luminescence of ytterbium(III) beta-diketonate complexes with 5-nitro-1,10-phenanthroline ancillary ligand: assessment of chain length and fluorination impact.


    Martín-Ramos, Pablo; Pereira da Silva, Pedro S; Lavín, Victor; Martín, Inocencio R; Lahoz, Fernando; Chamorro-Posada, Pedro; Silva, Manuela Ramos; Martín-Gil, Jesús


    Seven new tris(β-diketonear-nate)ytterbium(III) complexes with the general formula [Yb(β-diketonate)3(5NO2phen)] (where the β-diketone is either 4,4,4-trifluoro-1-(2-naphthyl)-1,3-butanedione, 4,4,4-trifluoro-1-(2-furyl)-1,3-butanedione, 1,1,1-trifluoro-2,4-pentanedione, 1,1,1-trifluoro-5,5-dimethyl-2,4-hexanedione, 1,1,1,5,5,6,6,7,7,7-decafluoro-2,4-heptanedione, 2,4-hexanedione or 2,6-dimethyl-3,5-heptanedione, and 5NO2phen = 5-nitro-1,10-phenanthroline) were synthesized and characterized by elemental analysis, attenuated total reflectance Fourier transform infrared spectroscopy and photoluminescence spectroscopy. Single crystal X-ray structures have been determined for three fluorinated complexes and ground state geometries of the other four complexes have been predicted using the Sparkle/PM6 model. These experimental structures and those designed by semi-empirical models reveal octacoordination around the Yb(3+) ion. Photoluminescence studies and lifetime measurements show that the increase in the fluorinated β-diketonate chain length is associated with a decrease in Yb(3+) luminescence intensity of the (2)F5/2→(2)F7/2 transition at around 980 nm and the (2)F5/2 excited state lifetime, while the ligand lifetime value remains almost unaffected. Finally, fluorination of the ligands is only advised when the complexes are to be used for co-doping with isostructural Er(3+) complexes for optical amplifiers, since it leads to a slight decrease in luminescence intensity for the same β-diketonate chain length. PMID:23900403

  9. Analysis of Redox Series of Unsymmetrical 1,4-Diamido-9,10-anthraquinone-Bridged Diruthenium Compounds.


    Mandal, Abhishek; Hoque, Md Asmaul; Grupp, Anita; Paretzki, Alexa; Kaim, Wolfgang; Lahiri, Goutam Kumar


    The unsymmetrical diruthenium complexes [(bpy)2Ru(II)(μ-H2L(2-))Ru(III)(acac)2]ClO4 ([3]ClO4), [(pap)2RuII(μ-H2L(2-))Ru(III)(acac)2]ClO4 ([4]ClO4), and [(bpy)2Ru(II)(μ-H2L(2-))Ru(II)(pap)2](ClO4)2 ([5](ClO4)2) have been obtained by way of the mononuclear precursors [(bpy)2Ru(II)(H3L(-))]ClO4 ([1]ClO4) and [(pap)2Ru(II)(H3L(-))]ClO4 ([2]ClO4) (where bpy = 2,2′-bipyridine, pap = 2-phenylazopyridine, acac(-) = 2,4-pentanedionate, and H4L = 1,4-diamino-9,10-anthraquinone). Structural characterization by single-crystal X-ray diffraction and magnetic resonance (nuclear magnetic resonance (NMR), electron paramagnetic resonance (EPR)) were used to establish the oxidation state situation in each of the isolated materials. Cyclic voltammetry, EPR, and ultraviolet-visible-near-infrared (UV-vis-NIR) spectroelectrochemistry were used to analyze the multielectron transfer series of the potentially class I mixed-valent dinuclear compounds, considering the redox activities of differently coordinated metals, of the noninnocent bridge and of the terminal ligands. Comparison with symmetrical analogues [L2′Ru(μ-H2L)RuL2′](n) (where L′ = bpy, pap, or acac(-)) shows that the redox processes in the unsymmetrical dinuclear compounds are not averaged, with respect to the corresponding symmetrical systems, because of intramolecular charge rearrangements involving the metals, the noninnocent bridge, and the ancillary ligands. PMID:26887785

  10. Continuous flow hydroformylation using supported ionic liquid phase catalysts with carbon dioxide as a carrier.


    Hintermair, Ulrich; Gong, Zenxing; Serbanovic, Ana; Muldoon, Mark J; Santini, Catherine C; Cole-Hamilton, David J


    A supported ionic liquid phase (SILP) catalyst prepared from [PrMIM][Ph(2)P(3-C(6)H(4)SO(3))] (PrMIM = 1-propyl-3-methylimidazolium), [Rh(CO)(2)(acac)] (acacH = 2,4-pentanedione) [OctMIM]NTf(2) (OctMIM = 1-n-octyl-3-methylimidazolium, Tf = CF(3)SO(2)) and microporous silica has been used for the continuous flow hydroformylation of 1-octene in the presence of compressed CO(2). Statistical experimental design was used to show that the reaction rate is neither much affected by the film thickness (IL loading) nor by the syngas:substrate ratio. However, a factor-dependent interaction between the syngas:substrate ratio and film thickness on the reaction rate was revealed. Increasing the substrate flow led to increased reaction rates but lower overall yields. One of the most important parameters proved to be the phase behaviour of the mobile phase, which was studied by varying the reaction pressure. At low CO(2) pressures or when N(2) was used instead of CO(2) rates were low because of poor gas diffusion to the catalytic sites in the SILP. Furthermore, leaching of IL and Rh was high because the substrate is liquid and the IL had been designed to dissolve in it. As the CO(2) pressure was increased, the reaction rate increased and the IL and Rh leaching were reduced, because an expanded liquid phase developed. Due to its lower viscosity the expanded liquid allows better transport of gases to the catalyst and is a poorer solvent for the IL and the catalyst because of its reduced polarity. Above 100 bar (close to the transition to a single phase at 106 bar), the rate of reaction dropped again with increasing pressure because the flowing phase becomes a better and better solvent for the alkene, reducing its partitioning into the IL film. Under optimised conditions, the catalyst was shown to be stable over at least 40 h of continuous catalysis with a steady state turnover frequency (TOF, mol product (mol Rh)(-1)) of 500 h(-1) at low Rh leaching (0.2 ppm). The selectivity of the

  11. The reactions of N-methylformamide and N,N-dimethylformamide with OH and their photo-oxidation under atmospheric conditions: experimental and theoretical studies.


    Bunkan, Arne Joakim C; Hetzler, Jens; Mikoviny, Tomáš; Wisthaler, Armin; Nielsen, Claus J; Olzmann, Matthias


    The reactions of OH radicals with CH3NHCHO (N-methylformamide, MF) and (CH3)2NCHO (N,N-dimethylformamide, DMF) have been studied by experimental and computational methods. Rate coefficients were determined as a function of temperature (T = 260-295 K) and pressure (P = 30-600 mbar) by the flash photolysis/laser-induced fluorescence technique. OH radicals were produced by laser flash photolysis of 2,4-pentanedione or tert-butyl hydroperoxide under pseudo-first order conditions in an excess of the corresponding amide. The rate coefficients obtained show negative temperature dependences that can be parameterized as follows: kOH+MF = (1.3 ± 0.4) × 10(-12) exp(3.7 kJ mol(-1)/(RT)) cm(3) s(-1) and kOH+DMF = (5.5 ± 1.7) × 10(-13) exp(6.6 kJ mol(-1)/(RT)) cm(3) s(-1). The rate coefficient kOH+MF shows very weak positive pressure dependence whereas kOH+DMF was found to be independent of pressure. The Arrhenius equations given, within their uncertainty, are valid for the entire pressure range of our experiments. Furthermore, MF and DMF smog-chamber photo-oxidation experiments were monitored by proton-transfer-reaction time-of-flight mass spectrometry. Atmospheric MF photo-oxidation results in 65% CH3NCO (methylisocyanate), 16% (CHO)2NH, and NOx-dependent amounts of CH2[double bond, length as m-dash]NH and CH3NHNO2 as primary products, while DMF photo-oxidation results in around 35% CH3N(CHO)2 as primary product and 65% meta-stable (CH3)2NC(O)OONO2 degrading to NOx-dependent amounts of CH3N[double bond, length as m-dash]CH2 (N-methylmethanimine), (CH3)2NNO (N-nitroso dimethylamine) and (CH3)2NNO2 (N-nitro dimethylamine). The potential for nitramine formation in MF photo-oxidation is comparable to that of methylamine whereas the potential to form nitrosamine and nitramine in DMF photo-oxidation is larger than for dimethylamine. Quantum chemistry supported atmospheric degradation mechanisms for MF and DMF are presented. Rate coefficients and initial branching ratios

  12. Surface modified carbon nanoparticle papers and applications on polymer composites

    NASA Astrophysics Data System (ADS)

    Ouyang, Xilian

    a tensile strength of 360 MPa and an electrical conductivity of 4.45x104 S/m, much better than any similar materials reported in the literature. However, they didn't show good gas barrier properties. Since the GO paper presented zero gas permeability for both CO2 and H2, a hybrid paper fabrication approach was proposed to combine the advantages of individual GP and GO papers. This was done by filtering GP and GO layer by layer with GO sandwiched in between two layers of GP. The resulting hybrid papers showed high mechanical tensile strength and EMI shielding effectiveness that are close to GP nanopapers, and excellent gas barrier properties that comparable to GO nanopapers. The GP, GO and GP-Go-GP hybrid nanopapers have been successfully coated onto the thermoplastic surface by thermal lamination and injection molding. In the third part, the effect of PANI-CNF nanopapers and a chelating agent, 2, 4- Pentanedione (2, 4-P) on kinetics of an in-mold coating (IMC) resin was investigated. The results showed that the presence of amine functionalized carbon nanoparticles tended to retard the resin reaction, while 2, 4-P was capable of promoting the redox based free radical polymerization by forming a complex with the cobalt promoter in the initiation step. In order to understand the chemical and physical changes during the resin curing process, kinetics study on two major resin components, i.e. hexanediol diacrylate (HDDA) and styrene (St), were carried out using an integrated analysis design: differential scanning calorimetry (DSC) for overall reaction, Fourier transform infrared spectroscopy (FTIR) for individual component reactions, and rheometry for liquid-solid transition during the reaction. The gel point of this radical polymerization resin system was found to be <2% which implied that most curing was conducted in the solid phase. The results showed that the double bonds in acrylates and St followed an azeotropic polymerization pattern.

  13. Reactions of heteroatom and carbon nucleophiles with the cationic bridging methylidyne complex

    SciTech Connect

    Casey, C.P.; Crocker, M.; Vosejpka, P.C.; Fagan, P.J.; Marder, S.R.; Gohdes, M.A.


    The reaction of the complex /((C/sub 5/H/sub 5/)(CO)Fe)/sub 2/( +/PF/sub 6//sup -/ (1) with NMe/sub 3/ and (C/sub 6/H/sub 5/)/sub 2/C=NH gave the cationic 1:1 adducts /((C/sub 5/H/sub 5/)(CO)Fe)/sub 2/( 3/)//sup +/PF/sub 6//sup -/ (3) and /((C/sub 5/H/sub 5/)(CO)Fe)/sub 2/( 6/H/sub 5/)/sub 2/)//sup +/PF/sub 6//sup -/ (9), respectively, arising from attack of nitrogen on the methylidyne carbon. The reaction of 1 with KOC(CH/sub 3/)/sub 3/ gave the neutral complex ((C/sub 5/H/sub 5/)(CO)Fe)/sub 2/( 3/)P/sub 3/) (4). Reaction of 1 with water afforded a 1:1 mixture of complex ((C/sub 5/H/sub 5/)(CO)Fe)/sub 2/( 2/) (2) and ((C/sub 5/H/sub 5/)(CO)Fe)/sub 2/( 2/; these products are proposed to arise from disproportionation of an initially formed hydroxy carbene species. Reaction of 1 with Et/sub 4/N/sup +/Br/sup -/ gave the unstable /sup +/-carbene complex ((C/sub 5/H/sub 5/)(CO)Fe)/sub 2/( (6). Reaction of 1 with the carbon nucleophiles CH/sub 3/Li and Li(C/sub 6/H/sub 5/CuCN) gave the complexes ((C/sub 5/H/sub 5/)(CO)Fe/sub 2/( 3/) (11) and ((C/sub 5/H/sub 5/)(CO)Fe)/sub 2/( 6/H/sub 5/ (12), while reaction of 1 with HFe(CO)/sub 4//sup -/ afforded 2. 1 reacted with acetone via nucleophilic addition of the enol affording the neutral complex (C/sub 5/H/sub 5/)-(CO)Fe)/sub 2/( 2/COCH/sub 3/)) (13). 1 also reacted with cyclohexanone, 2-butanone, 4-methyl-2-pentanone, 2,4-pentanedione, 5,5-dimethyl-1,3-cyclohexanedione, ethyl acetoacetate, and the sodium salt of diethyl malonate to give similar products.

  14. Volatile organic compounds in the marine troposphere and surface oceans: methods, measurements and biogeochemical implications

    NASA Astrophysics Data System (ADS)

    Hudson, Edward


    first optimized for acetone and subsequently for a suite of 23 C1 -- C9 carbonyl compounds. The buffering capacity of seawater necessitated the use of artificial seawater for standard preparation, and acidification of seawater samples to achieve the method's optimum pH of 3.7. Sparging with UHP argon, and C-18 solid phase extraction of the dissolved PFBHA, were found to be the most effective methods for reducing the high process blanks observed for C1-C3 carbonyl compounds. Using this technique, the first acetone measurements for North Atlantic and Arctic waters (5.5 --9.6 nM acetone), the first surface water measurements of carbonyl compounds from the St. Lawrence Estuary (including glyoxal, methylglyoxal and 2,4-pentanedione), and concentrations of 11 C1 - C9 carbonyl compounds in surface seawaters from the Labrador Sea and from the Scotian Shelf were reported. This represents the first survey of these compounds in seawaters outside of the tropics. The results suggest that the North Atlantic is a sink for glyoxal and formaldehyde. Fluxes of several C4 - C9 aldehydes from the ocean to the atmosphere were estimated to be -13 to +14 mumol/m2/day.