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71.
V. A. Zakharov N. V. Semikolenova T. B. Mikenas A. A. Barabanov G. D. Bukatov L. G. Echevskaya M. A. Mats’ko 《Kinetics and Catalysis》2006,47(2):303-309
Data on ethylene polymerization on homogeneous and supported catalysts based on 2,6-bis(imino)pyridyl Fe(II) complexes activated by trialkylaluminums are considered (activity, the molecular-weight characteristics of polymers, the number of active sites, and the propagation rate constants). Unlike homogeneous systems, the supported catalysts prepared with the use of various carriers (SiO2, Al2O3, and MgCl2) exhibited high stability and activity at 70–80°C and produced high-molecular-weight polyethylene with a broad molecular-weight distribution (MWD). The molecular weights and MWDs of polymers and the propagation rate constant depended on the nature of the carrier only slightly. The reasons for an unusual effect of an increase in the activity of the supported catalysts in ethylene polymerization in the presence of hydrogen are discussed. 相似文献
72.
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73.
Lisachenko A. A. Kuznetsov V. N. Zakharov M. N. Mikhailov R. V. 《Kinetics and Catalysis》2004,45(2):189-197
A combined study of intrinsic structural defects in reduced TiO2 was performed using mass spectrometry, optical diffuse-reflectance spectroscopy, and UV photoelectron spectroscopy (UPS). It was found that the reduction of TiO2 resulted in the appearance of absorption in the region 0.50 h 3.50 eV (400 2500 nm), which is formed by absorption due to free electrons (a continuum at h 1.50 eV), local centers—Ti3+ ions (a band at 2.00 eV), and oxygen vacancies (bands at 1.17, 2.81, and 2.55 eV). The spectrum of induced occupied electronic states in the forbidden gap and the position of oxygen vacancy levels with respect to the Fermi level were determined by UPS. The absorption of reduced TiO2 was stable on the sample to T = 800 K in a vacuum; however, it weakened in contact with O2, NO, and N2O molecules beginning at T = 300 K (surface sites) and T 400 K (subsurface sites) as a result of filling oxygen vacancies with atomic oxygen in the course of dissociative adsorption. The adsorption complexes formed by the interaction of O2, NO, and N2O with defects were analyzed by temperature-programmed desorption. The distribution of sites over the energies of oxygen binding was found with the use of a nonuniform surface model, and specific oxygen adsorption species were revealed. It was found that the irradiation of TiO2 activates the formation and decay of sites and results in the formation of specific O2 and N2O adsorption species. 相似文献
74.
Hughes RP Meyer MA Tawa MD Ward AJ Williamson A Rheingold AL Zakharov LN 《Inorganic chemistry》2004,43(2):747-756
Reaction of Pd(TMEDA)(CH(3))(2) [TMEDA = tetramethylethylenediamine] with fluoroalkyl iodides R(F)I affords a series of square planar Pd(II) complexes Pd(TMEDA)(CH(3))(R(F)) [R(F) = CF(2)CF(3) (9), CFHCF(3) (10), CH(2)CF(3) (11)], presumably by oxidative addition followed by reductive elimination of CH(3)I. The solid-state structures of each compound have been determined by single crystal X-ray diffraction studies, allowing the effect of increasing alpha-fluorination on the structural trans-influence of alkyl ligands to be examined. In these compounds there is no significant difference observed in the trans-influence of the three fluorinated alkyl ligands toward the trans-N atom, although a significant cis-influence on the neighboring methyl ligand is apparent. Oxidative addition of the same series of fluoroalkyl ligands to the corresponding Pt(TMEDA)(CH(3))(2) affords octahedral Pt(IV) complexes trans-Pt(TMEDA)(CH(3))(2)(R(F))I [R(F) = CF(2)CF(3) (12), CFHCF(3) (13), CH(2)CF(3) (14)] as the kinetic products. In each case, subsequent isomerization to the corresponding all cis-isomers is observed; in the case of 13, the stereocenter at the alpha-carbon results in two diastereomeric cis-isomers, which are formed at different rates. The molecular structures of 13 and its more stable all cis-isomer 16b have been crystallographically determined. Kinetic studies of the trans-cis isomerization reactions show the mechanism to involve a polar transition state, presumably involving iodide dissociation, followed by rearrangement of the cation, and iodide recombination. High dielectric solvents increase the rate, but solvent coordinating ability has no effect. Dissolved salts (LiI, LiOTf) show normal accelerative salt effects, with no inhibition in the case of added iodide, consistent with the formation of an intimate ion pair intermediate. The kinetic parameters show that the trans-effects of fluoroalkyl ligands in these compounds follow the order expected from the relative sigma-donor properties of the ligands, with CF(2)CF(3) < CFHCF(3) < CH(2)CF(3). 相似文献
75.
A. A. Trifonov L. N. Zakharov M. N. Bochkarev Yu. T. Struchkov 《Russian Chemical Bulletin》1994,43(1):145-148
Ytterbium complexes, Cp2Yb(-2:2-DAB)Li(DME) (1) and CpYb(DAB)K(THF)2 (2), containing a bridging diazadiene ligand were prepared by the reaction of CpYbCl2(THF)3 with (DAB)Li2 (11) and (DAB)–K+ (12) (DAB = But-N=CH-CH=N-But). The structure of complex1 was established by X-ray diffraction analysis. The complex is binuclear: the Yb atom of the Cp2Yb fragment and the Li atom, which is bonded as well with the chelating DME molecule, are linked by the DAB ligand.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 148–151, January, 1994. 相似文献
76.
Sharutin V. V. Sharutina O. K. Osipov P. E. Platonova T. P. Pakusina A. P. Fukin G. K. Zakharov L. N. 《Russian Journal of Coordination Chemistry》2001,27(7):483-485
2-tert-Butylphenoxytetraphenylantimony Ph4SbOC6H4(Bu-t)-2 was prepared by the reaction of pentaphenylantimony with 2-tert-butylphenol in toluene at 20°. The structure of the obtained compound was determined by X-ray diffraction. The Sb atom in this compound has a distorted trigonal-bipyramidal coordination with the aroxy group in the axial position. The Sb–C(Ph)eqand Sb–C(Ph)axdistances are 2.111(7)–2.138(7) and 2.180(7) Å the Sb–O and O–CArdistances are 2.143(4) and 1.363(8) Å, respectively. The C(Ph)axSbOAraxial angle is 174.1(2)°, while the SbOC angle is 126.7(4)°. 相似文献
77.
V. P. Zakharov Kh. A. Aslanov A. I. Ishbaev A. S. Sadykov B. A. Yankovskii 《Chemistry of Natural Compounds》1976,10(4):474-476
Summary 1. The optimum conditions for the extraction of the high-boiling alkaloids from technical anabasine sulfate by dilution with water and at various pH values of the medium have been established.2. A method for removing anabasine and lupinine from a mixture of the high-boiling alkaloids ofAnabasis aphylla has been developed which is based on the formation of the carbonates of the strong bases.V. I. Lenin Tashkent State University. Dzerzhinskii Chimkent Pharmaceutical Chemicals Factory. Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 468–472, July–August, 1974. 相似文献
78.
Zakharov S. V. Nuriazdanova G. Kh. Garifzyanov A. R. Galkin V. I. Cherkasov R. A. 《Russian Journal of General Chemistry》2004,74(6):873-881
-Aminophosphoryl compounds of the phosphonate, phosphine oxide, and ,-bis(phosphine oxide) series and some of their thiophosphoryl analogs were synthesized. Potentiometric measurements of the pKa of the conjugate acids revealed an insignificant effect of variation of substituents on the phosphorus, nitrogen, and -carbon atoms on the basicity of the phosphorylated amines. The latter are weak bases. Organophosphorus groups decrease the basicity of the amines by almost 5 pK
a units. The role of the hydrophobic effect and intramolecular H-bonding in the obtained substances was discussed. 相似文献
79.
80.
Sokolov MN Gushchin AL Virovets AV Peresypkina EV Kozlova SG Fedin VP 《Inorganic chemistry》2004,43(25):7966-7968
Black single crystals of Ta(4)Se(9)I(8) are obtained in a high yield by heating Ta, Se, and I(2) at 300 degrees C in 1:2.2:1.0 molar ratio. In the structure, the tantalum atoms form a square, with four Se(2) ligands bridging the Ta-Ta edges and one capping the square. Each Ta atom has two terminal iodine atoms. The compound is diamagnetic and has only two electrons for metal-metal bonding. 相似文献