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91.
Kraikivskii P. B. Saraev V. V. Matveev D. A. Zelinskii S. N. Tkach V. S. 《Russian Journal of Coordination Chemistry》2003,29(6):431-434
Reactions of aluminium tribromide with the Ni(0) phosphine and phosphite complexes are studied by EPR method. AlBr3was found to cause the oxidation of the transition metal in the (PPh3)4Ni complex to the univalent state with the formation of the tetracoordinated (PPh3)3NiBr complex. With an excess of AlBr3, the phosphine ligands are eliminated from the coordination sphere of Ni(I), and the coordinatively unsaturated complexes are destroyed to give the colloidal nickel. In the reaction of (P(OEt)3)4Ni with AlBr3, Ni(0) is also oxidized to Ni(I), but the acido ligand is not eliminated even with a 15-fold excess of the Lewis acid. The activity of catalytic systems on the basis of the Ni(0) phosphine complexes and the Lewis acids in the low-molecular oligomerization reactions of olefines is determined by the cationic coordinatively unsaturated Ni(I) complexes formed in these systems. 相似文献
92.
Mikhail D. Borisover Felix D. Baitalov Boris N. Solomonov 《Journal of solution chemistry》1995,24(6):579-586
A new method was suggested for estimating the hydrophobic effect of contributions to the Gibbs energies and enthalpies of hydration of hydrocarbons, inorganic gases and rare gases. In accordance with this method the hydrophobic effect contribution to the Gibbs energy was evaluated from the difference between the hydration Gibbs energy of a solute and the non hydrophobic contribution. To estimate the latter value, the known dependence connecting the Gibbs energies of solvation of a solute in a number of aprotic solvents to the Hildebrand solubility parameter for these solvents was used. The non hydrophobic contribution to the Gibbs energy of hydration was calculated for various solutes from such dependences extended to water as solvent. The Hildebrand solubility parameter for water used in the calculation was corrected for the effect of association through hydrogen bonding. This correction was made by subtraction of the water self-association enthalpy from the enthalpy of vaporization of water. The evaluated Gibbs energies of the hydrophobic effect are positive for saturated hydrocarbons, inorganic gases and rare gases and linearly depend on the solute molecular refraction. The hydrophobic contribution to the hydration enthalpies of the solutes was calculated in the same manner as was made to calculate the hydrophobic contribution to Gibbs energies of hydration. Enthalpies of the hydrophobic effect for the solutes under study are negative. 相似文献
93.
G. U. Mennenga A. I. Rudenkov K. I. Matveev I. V. Kozhevnikov 《Reaction Kinetics and Catalysis Letters》1976,5(4):401-406
Oxidative coupling of alkylbenzenes (benzene, toluene, o-xylene, durene) is shown to proceed in the presence of palladium salts and heteropolyacids under the action of oxygen with a high yield of diaryls. The addition of mercury salts and variation of the solvent affect the reaction rate and isomer composition of the products.
, (, , -, ) . .相似文献
94.
V. E. Tarabanko I. V. Kozhevnikov K. I. Matveev 《Reaction Kinetics and Catalysis Letters》1978,8(1):77-79
Oxidative coupling of thiophene and 2-methylfuran to the corresponding dihetaryls in DMFA medium occurs in the presence of the homogeneous catalytic system Pd(II)-molybdovanodophosphoric heteropolyacid (HPA). The data obtained show that HPA may act as a reversible oxidant in polar aprotic media.
, Pd(II)- 2- . , .相似文献
95.
Elena G. Zhizhina Marina V. Simonova Viktor F. Odyakov Klavdiy I. Matveev 《Reaction Kinetics and Catalysis Letters》2006,89(1):157-166
Summary Oxidation of propene to acetone in water solutions in the presence of homogeneous catalysts (Pd2+ + HPA-x, where HPA-x = H3+xPVxMo12-xO40, x = 1-4) is studied. This reaction is shown to be of the 1st order with respect to C3H6 and of the 0.5th order with respect to Pd. The reaction rate does not depend on the concentration of HPA-x and acidity of
the catalyst solution. The apparent activation energy of the reaction is 21 kJ/mol. A reaction mechanism is proposed. 相似文献
96.
High resolution HF product time-of-flight spectra measured for the reactive scattering of F atoms from n-H2(p-H2) molecules at collision energies between 69 and 81 meV are compared with exact coupled-channel quantum mechanical calculations based on the Stark-Werner ab initio ground state potential energy surface. Excellent agreement between the experimental and computed rotational distributions is found for the HF product vibrational states v'=1 and v'=2. For the v'=3 vibrational state the agreement, however, is less satisfactory, especially for the reaction with p-H2. The results for v'=1 and v'=2 confirm that the reaction dynamics for these product states is accurately described by the ground electronic state 1 (2)A' potential energy surface. The deviations for HF(v'=3, j' > or =2) are attributed to an enhancement of the reaction resulting from the 25% fraction of excited ((2)P(12)) fluorine atoms in the reactant beam. 相似文献
97.
Mikhail Katz 《Geometriae Dedicata》1991,40(2):171-190
We study the critical points of the diameter functional on the n-fold Cartesian product of the complex projective plane C
P
2 with the Fubini-Study metric. Such critical points arise in the calculation of a metric invariant called the filling radius, and are akin to the critical points of the distance function. We study a special family of such critical points, P
kC
P
1C
P
2, k=1,2... We show that P
k is a local minimum of by verifying the positivity of the Hessian of (a smooth approximation to) at P
k. For this purpose, we use Shirokov's law of cosines and the holonomy of the normal bundle of C
P
1C
P
2. We also exhibit a critical point of , given by a subset which is not contained in any totally geodesic submanifold of C
P
2. 相似文献
98.
In the course of comparing the reaction chemistry of (C5Me5)3U, 1, and its slightly less crowded analogue (C5Me4H)3U, 2, new syntheses of UI3, (C5Me4H)3U, (C5Me4H)3UCl, 3, and (C5Me5)3UCl, 4, have been developed. Additionally, (C5Me4H)3UI, 5, and (C5Me4H)2UCl2, 6, have been identified for the first time. A facile synthesis of unsolvated UI3 is reported that proceeds in high yield with inexpensive equipment from iodine and hot uranium turnings. Both UI3 and UI3(THF)4 react with KC5Me4H in toluene to make unsolvated (C5Me4H)3U in higher yield than in previous reports that involve reduction of tetravalent (C5Me4H)3UCl, 3. A more atom-efficient synthesis of complex 3 is also reported that proceeds from reduction of t-BuCl, PhCl, or HgCl2 by 2. Similarly, (C5Me4H)3U reacts with PhI or HgI2 to generate (C5Me4H)3UI. These studies also provided a basis to improve the synthesis of (C5Me5)3UCl from 1 by employing t-BuCl or HgCl2 as the halide source. Like (C5Me5)3UCl, the (C5Me4H)3UCl complex reacts with HgCl2 to form (C5Me4H)2 and (C5Me4H)2UCl2, 6, but unlike (C5Me5)3UX (X = Cl or I), the less substituted (C5Me4H)3UX complexes do not reduce t-BuCl or PhX. The synthesis of 6 from (C5Me4H)MgCl x THF and UCl4 is also included. 相似文献
99.
Victor N. Khrustalev Mikhail Yu. Antipin Irina V. Borisova Valery V. Lunin Ghassoub Rima 《Journal of organometallic chemistry》2004,689(2):478-483
The reaction of equimolar quantities of LiOCH2CH2NMe2 and E14(OCH2CH2NMe2)2 (E14=Ge, Sn) in ether yielded new ate complexes [LiE14(OCH2CH2NMe2)3]2 (E14=Ge (1), Sn (2)) with bidentate ligands. The compounds 1 and 2 are white crystalline substances which are highly soluble in THF and pyridine and very sensitive to the traces of oxygen and moisture. The structures of these compounds are studied by X-ray diffraction analysis. The ate complexes 1 and 2 are powerful nucleophiles and may be employed as ligands (neutral) in the coordination chemistry of the transition metals. The electronegative O-substituents at the divalent E14 atoms render them less oxidizable than alkyl- or aryl-substituted derivatives, and the bidentate ligands, owing to intramolecular donor-acceptor interactions, make them more thermodynamically stable compared to monodentate ligands. 相似文献
100.
Anatoli Korkin Mikhail Glukhovtsev Paul von Ragu Schleyer 《International journal of quantum chemistry》1993,46(1):137-144
Silicon analogs of aromatic monocyclic ions, (SiH) ( 4 ), (SiH) ( 5 ), and (SiH) ( 6 ) have been studied ab initio at MP 2(full)/6-31G *. The D3h structure of Si3H3+ is the global minimum, whereas other two ions are nonplanar. The D2d structure of (SiH) is less folded than the carbon analog and possesses a higher stabilization energy. Stabilization energies for the monocharged ions are diminished with respect to the corresponding carbons © 1993 John Wiley & Sons, Inc. 相似文献