Ab initio Calculations for the Addition of Ethylene to Metal-Hydrogen and Metal-Methyl Bonds in Hydride and Alkyl Complexes of Ti, Al, and B Full article
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Kinetics and Catalysis
ISSN: 0023-1584 , E-ISSN: 1608-3210 |
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Output data | Year: 1994, Volume: 35, Number: 1, Pages: 64-71 Pages count : 8 | ||
Tags | HOMOGENEOUS OLEFIN POLYMERIZATION; PAIRED INTERACTING ORBITALS; TRANSITION-METALS; INSERTION; CATALYSIS; PROPYLENE; MOLECULES; ALUMINUM; TITANIUM; STATE | ||
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Abstract:
The addition of ethylene to the metal-hydrogen and metal-methyl bonds in the complexes H2MR (M = Ti, Al, B; R = H, CH3) is investigated by the ab initio SCF MO LCAO quantum-chemical method with a split-valence basis set of Gaussian functions. The structure of a transition state for the addition of coordinated ethylene and the energy profile for the general reaction of ethylene addition are calculated. The role of electronic and steric factors in this reaction is analyzed using boron complexes as an example. It is shown that the electronic mechanism of the insertion of ethylene into the M-R bond is determined by the electron-density transfer from the sigma-bonded orbital of the M-R bond to the pi*-antibonding orbital of ethylene. A concept is suggested that attributes the chemical reactivity of the M-R bonds to the relation of s-, p-, and d-orbital interactions contributing to the bond formation. The activation energy is increased with increasing s character and is decreased with increasing d character.
Cite:
Zakharov I.I.
, Zakharov V.A.
, Zhidomirov G.M.
Ab initio Calculations for the Addition of Ethylene to Metal-Hydrogen and Metal-Methyl Bonds in Hydride and Alkyl Complexes of Ti, Al, and B
Kinetics and Catalysis. 1994. V.35. N1. P.64-71. WOS РИНЦ
Ab initio Calculations for the Addition of Ethylene to Metal-Hydrogen and Metal-Methyl Bonds in Hydride and Alkyl Complexes of Ti, Al, and B
Kinetics and Catalysis. 1994. V.35. N1. P.64-71. WOS РИНЦ
Original:
Захаров И.И.
, Захаров В.А.
, Жидомиров Г.М.
Неэмпирические расчеты реакции присоединения этилена по связям металл-водород и металл-метил в гидридных и алкильных комплексах Ti, Al и B
Кинетика и катализ. 1994. Т.35. №1. С.74-82. РИНЦ
Неэмпирические расчеты реакции присоединения этилена по связям металл-водород и металл-метил в гидридных и алкильных комплексах Ti, Al и B
Кинетика и катализ. 1994. Т.35. №1. С.74-82. РИНЦ
Dates:
Submitted: | Mar 12, 1993 |
Identifiers:
Web of science | WOS:A1994NE85400009 |
Elibrary | 29284531 |