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31.
Zn3V3O8 two-dimensional micro sheets are successfully synthesized by combination of solvothermal method and heat treatment. The Zn3V3O8 has better electrochemical performances after calcinations. 相似文献
32.
Lorraine P. McDonnell Bushnell Eric R. Evitt Robert G. Bergman 《Journal of organometallic chemistry》1978,157(4):445-456
Reactions of η5-cyclopentadienylbis(triphenylphosphine)cobalt(I) (5) with several 2,n-alkadiynes (2) were investigated. Each of these reactions leads initially to a material in which one of the acetylene functional groups is π-coordinated to cobalt; this complex then undergoes conversion to a metallocycle. In cases where the two acetylene functions are connected by three- and four-carbon bridges (2b, 2c), metallocycles formed by intramolecular reaction of two acetylene functions in the same molecule may be isolated. In cases where the acetylene functions are joined by larger or smaller bridges, the reactions are more complex, and both inter- and intramolecular metallocycles are formed. Reactions of 5 with 1,8-bis(trimethylsilyl)-1,7-octadiyne (16) gives an isolable crystalline mono-acetylene complex (17), this material is stable in the solid state but undergoes conversion to metallocycle (18) in benzene solution. The relationship of these results to the mechanism of the CpCo(CO)2-catalyzed benzocycloalkene synthesis is discussed; it is suggested that intramolecular metallocycles are intermediates in reactions leading to benzocyclopentanes and -cyclohexenes, but intermolecular metallocycles are probably involved in reactions leading to benzocyclobutenes. 相似文献
33.
trans-Pd(NO3)H(PCy3)2 (I) when treated with Et4NCl forms the hydride trans-PdClH(PCy3)2 which in turn reacts with AgPF6 in acetonitrile to give trans-[PdH(CH3CN)(PCy3)2]PF6 (III). Both I and III react smoothly with acetylenes containing one electron-withdrawing group to give alkenyl products. The geometry of the resulting alkenyl ligand implies that cis addition has occurred and that the hydridic hydrogen adds to the acetylenic carbon containing the electron-withdrawing group.Acetylenes containing two electron-withdrawing groups give mixtures from which both alkenyl and zerovalent acetylene compounds can sometimes be isolated. In the presence of proton sponge, monosubstituted acetylenes still give alkenyl products while those substituted with two electron-withdrawing groups give the zerovalent products in good yield. The relevance of these results to an understanding of the nature of the migratory insertion reaction is discussed. 相似文献
34.
The reactions of Fe(CO)5, Fe(CO)4P(C6H5)3, M(CO)6 (M W, Mo, Cr), and (CH3C5H4Mn(CO)3 with KH and several boron and aluminium hydrides were investigated. Iron pentacarbonyl was converted quantitatively to K+Fe(CO)4-(CHO) by hydride transfer from KBH(OCH3)3 allowing isolation of [P(C6H5)3]2-Nn+Fe(CO)4(CHO)? in 50% yield. Lower yields were obtained with LiBH(C2H5)3, and other hydride sources gave little or no formyl product. The stability of Fe(CO)4(CHO)? in THP was found to depend on the cation, decreasing in the order [P(C6H5)3]2N+ > K+ > Na+ > Li+. No formyl complexes were isolated and no spectroscopic evidence for formyl formation was observed in the reactions of the other transition metal carbonyls with several hydride sources. Fe(CO)4-P(C6H5)3 gave K2Fe(CO)4 when treated with KHB(OCH3)3. When treated with LiBH(C2H5)3, W(CO)6 gave a mixture of HW2(CO)10?and (OC)5W(COC2H5)?; the latter was methylated to give the carbene complex (OC)5WC(OCH3)C2H5. 相似文献
35.
Jun?ZhangEmail author Pei-Hong?Deng Yong-Lan?Feng Yun-Fei?Kuang Jin-Jun?Yang 《Mikrochimica acta》2004,147(4):279-282
A carbon black microelectrode modified by -MnO2 has been prepared. The electrocatalytical oxidation of ascorbic acid (AA) at this microelectrode was investigated. The 2nd-order linear scan voltammograms of AA are recorded from –0.5 to 0.5V (vs. SCE). The relationship between the oxidation peak current of AA and its concentration in the range of 1.0×10–64.0×10–3molL–1 is linear. The detection limit (3) was found to be 6.0×10–7molL–1. Also, the determination of AA in samples is evaluated, and the results are satisfactory. 相似文献
36.
Ewa?Cholewa Ian?Burgess Julia?Kunze Jacek?LipkowskiEmail author 《Journal of Solid State Electrochemistry》2004,8(10):693-705
Electrochemical measurements including cyclic voltammetry, differential capacity, and chronocoulometry have been used to characterize the adsorption behaviors of the zwitterionic surfactant
N-dodecyl-N,N-dimethyl-3-ammonio-1-propanesulfonate (DDAPS) on the Au(111) electrode surface. The thermodynamics of the ideally polarized electrode have been employed to determine the Gibbs excess and the Gibbs energy of adsorption. The results show that the adsorption of DDAPS has a multistate character. The first two states are observed at potentials close to zero charge. At low bulk DDAPS concentrations, it corresponds to the formation of a film of nearly flat adsorbed molecules. At higher concentrations it is converted into a hemimicellar state. The second state is formed at negative potentials and charge densities close to 0 C cm–2. It corresponds to a film of tilted molecules oriented with the hydrocarbon tail towards the metal and the polar head toward the solution.Dedicated to Professor Zbigniew Galus on the occasion of his 70th birthday and in recognition of his many contributions to electrochemistry. 相似文献
37.
The Electron impact mass spectra of (CO)3 MC6H5—X complexes (M = Cr, W; X = OCH3, OC4H9, CO2CH3, CO2C4H9) were recorded. From metastable transitions and by high-resolution measurements complete fragmentation diagrams were obtained; in some cases comparative structure determinations of fragment ions were carried out by collisional activation. The fragmentation of the tungsten complexes considerably differs from that of the chromium compounds. The differences may be attributed to the stronger-electrophilic character as well as to the more pronounced tendency of tungsten to attain higher oxidation states. 相似文献
38.
E.B. Lobkovskii G.L. Soloveichik A.I. Sisov B.M. Bulychev A.I. Gusev N.I. Kirillova 《Journal of organometallic chemistry》1984,265(2):167-173
The structure of a titanium aluminium hydride complex of composition [(C5H5)2TiAlH4]2(CH3)2NC2H4N(CH3)2C6H6 has been determined by X-ray diffraction. The complex forms triclinic crystals with unit cell dimensions a = 8.406(2), b = 10.117(2), c = 11.269(3) Å; α = 112.01(2)°, β = 109.25(2)°, γ = 87.04(2)°, space group P, Z = 2 and density d = 1.21 g/cm3. The structure was refined to give a discrepancy index R = 0.056. The crystals are composed of centrosymmetric molecules of (Cp2TiAlH4)2TMEDA (Cp = η5-cyclopentadienyl) and molecules of crystal benzene. Two moieties of Cp2TiH2AlH2 are linked by a tetramethylethylenediamine molecule (rAlN 2.11 Å). The aluminium atom is bonded to a titanium atom by a double hydride bridge (rAlH b = 1.8, 1.6 Å, rTiH b = 1.6 Å), and has trigonal bipyramidal stereochemistry, [H4N] (rAlH t = 1.6 Å). 相似文献
39.
Ab initio calculations ofp-dichlorobenzene molecule were carried out using the Hartree-Fock method in the 6–31 G* valence-split basis set. The molecule was also calculated by the MNDO method in the valence sp-basis set for comparison. The populations of the valent p-orbitals of the C and CI atoms were analyzed. The optimized geometry of the molecule as well as its35Cl NQR frequency and the asymmetry parameter of the electric field gradient at the35CI nuclei calculated using the populations of the less diffuse components of the valent p-orbitals of the Cl atoms are in agreement with the corresponding experimental values for the -modification of 1,4-Cl2C6H4.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 2177–2179, September, 1996. 相似文献
40.
The proton NMR spectra of N-[2-pyridyl-N-oxide]-derivatives of primary and secondary ethylamines, containing a substituent R on the C atom bearing the amino function, have been completely analysed in terms of the fundamental NMR parameters. The preferred conformations of the compounds investigated were established by the indications from NOE experiments as well as: (1) the long range coupling across the five bond between the aminic hydrogen and the proton in 4-position of the pyridine-N-oxide ring (5JmH,NH ~ 0·5 c/s), (2) the value of the vicinal coupling constant in the fragment CHNH (3JNHCH ~ 7–9 c/s), (3) the large deshielding (Δτ ~ 1–1·5 ppm) observed for the resonance position of the proton on the asymmetric C atom in secondary amine derivatives with respect to the corresponding primary ones, and (4) the diamagnetic shielding produced on protons in position 3 and 4 of the pyridine-N-oxide ring by different aromatic groups introduced in the R substituent.The NMR data confirmed the preferred rotamers previously suggested on the basis of ORD and CD measurements. 相似文献