A Quantum-Chemical Study of β-Hydride Transfer Reactions for Titanium-Containing Active Sites in Olefin Polymerization Научная публикация
Журнал |
Kinetics and Catalysis
ISSN: 0023-1584 , E-ISSN: 1608-3210 |
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Вых. Данные | Год: 1996, Том: 37, Номер: 1, Страницы: 41-45 Страниц : 5 | ||
Ключевые слова | ZIEGLER-NATTA POLYMERIZATION; MECHANISM; ETHYLENE; ALUMINUM | ||
Авторы |
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Организации |
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Реферат:
Reactions of beta-hydride elimination from complexes H(2)MCH(2)CH(3) (M = Ti or Al) were studied by the ab initio SCF MO LCAO method using a valence-split Gaussian basis set. These reactions correspond to the processes of beta-hydride transfer to the metal or coordinated ethylene in the catalytic polymerization of ethylene. The transition-state structures and energy profiles of these reactions were calculated. It was shown that the activation energy for the reactions of transfer to the monomer is lower than for the reactions of beta-hydride transfer to the metal atom. On the basis of the concept of stability (aromaticity) of the transition state, it was suggested that the ratio between the reactivities in the reactions of chain,growth and termination is defined by the ratio between the contributions of the s and d orbitals of the active site to the formation of the metal-alkyl bond. In regards to this suggestion, the effect of the nature of the metal atom (Ti or Al) on the ratio between the reaction rates of polymer chain growth and termination was explained.
Библиографическая ссылка:
Zakharov I.I.
, Zakharov V.A.
, Zhidomirov G.M.
A Quantum-Chemical Study of β-Hydride Transfer Reactions for Titanium-Containing Active Sites in Olefin Polymerization
Kinetics and Catalysis. 1996. V.37. N1. P.41-45. WOS Scopus РИНЦ
A Quantum-Chemical Study of β-Hydride Transfer Reactions for Titanium-Containing Active Sites in Olefin Polymerization
Kinetics and Catalysis. 1996. V.37. N1. P.41-45. WOS Scopus РИНЦ
Оригинальная:
Захаров И.И.
, Захаров В.А.
, Жидомиров Г.М.
Квантово-химическое исследование реакций β-гидридного переноса для титансодержащих активных центров в полимеризации олефинов
Кинетика и катализ. 1996. Т.37. №1. С.46-50. РИНЦ
Квантово-химическое исследование реакций β-гидридного переноса для титансодержащих активных центров в полимеризации олефинов
Кинетика и катализ. 1996. Т.37. №1. С.46-50. РИНЦ
Даты:
Поступила в редакцию: | 16 нояб. 1994 г. |
Идентификаторы БД:
Web of science | WOS:A1996TY56500007 |
Scopus | 2-s2.0-0040988063 |
РИНЦ | 13230959 |
Chemical Abstracts | 1996:149019 |
Chemical Abstracts (print) | 124:203175 |