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A study of the oxidative addition of methane and fluoromethane to nickel, palladium, and platinum atoms and zero-valent phosphine complexes by density functional theoryстатья
Информация о цитировании статьи получена из
Web of Science,
Scopus
Статья опубликована в журнале из списка Web of Science и/или Scopus
Дата последнего поиска статьи во внешних источниках: 18 июля 2013 г.
- Авторы: Smurnyi E.D., Gloriozov I.P., Ustynyuk Y.A.
- Журнал: Russian Journal of Physical Chemistry A
- Том: 77
- Номер: 10
- Год издания: 2003
- Издательство: Pleiades Publishing, Ltd
- Местоположение издательства: Road Town, United Kingdom
- Первая страница: 1699
- Последняя страница: 1708
- Аннотация: The oxidative addition of methane and fluoromethane to nickel, palladium, and platinum atoms and to their diphosphine and ethylenediphosphine complexes was studied using a unique approach by the density functional theory with the PBE functional and the TZ2p basis set taking into account relativistic corrections (the SBK effective core potential). The complete reaction paths were determined, and the saddle points were identified by calculating the Hessians. The reactions under consideration (except the dissociation of the C-H bond with the participation of atomic platinum, which was a barrierless reaction) involved the stage of formation of donor-acceptor prereaction complexes. The electrophilic and nucleophilic reaction phases were discovered. The barriers to reactions were found to decrease, and the heats of reactions to increase along the series of metals Pd. Ni. Pt, and along the series of complexes M(PH3)(2), M(PH2CH2CH2PH2). Fluoromethane was more active than methane. The conclusion was drawn that the oxidative addition of fluoromethane at the C-H bond was a kinetically controlled reaction, and the addition at the C-F bond was more favorable under thermodynamically controlled conditions.
- Добавил в систему: Глориозов Игорь Павлович