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A quantum-chemical study of β-hydride transfer reactions for titanium-containing active sites in olefin polymerizationстатья
Информация о цитировании статьи получена из
Scopus,
Web of Science
Статья опубликована в журнале из списка Web of Science и/или Scopus
Дата последнего поиска статьи во внешних источниках: 18 июля 2013 г.
- Авторы: Zakharov I.I., Zakharov V.A., Zhidomirov G.M.
- Журнал: Kinetics and Catalysis
- Том: 37
- Номер: 1
- Год издания: 1996
- Издательство: Maik Nauka/Interperiodica Publishing
- Местоположение издательства: Russian Federation
- Первая страница: 41
- Последняя страница: 45
- Аннотация: Reactions of β-hydride elimination from complexes H2MCH2CH3 (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 β-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 β-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.
- Добавил в систему: Жидомиров Георгий Михайлович