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Kinetics of protonation of tungsten hydrides WH(CO)(2)(NO)L-2 by weak OH-acidsстатья
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 марта 2017 г.
- Авторы: Belkova N.V., Epstein L.M., Krylova A.I., Faerstein E.G., Shubina E.S.
- Журнал: Russian Chemical Bulletin
- Том: 56
- Номер: 5
- Год издания: 2007
- Издательство: Springer Nature
- Местоположение издательства: Switzerland
- Первая страница: 870
- Последняя страница: 874
- DOI: 10.1007/s11172-007-0131-z
- Аннотация: The kinetics of protonation of tungsten hydrides WH(CO)2(NO)L2 (1, L = PMe3, PEt3, P(OPri)3, PPh3) by weak OH-acids (PhOH, (CF3)2CHOH, (CF3)3COH) in hexane was studied by IR spectroscopy. The study of the reactions of compounds 1 with OH-acids at 190–270 K revealed that the first step involves the formation of dihydrogen-bonded W(CO)2(NO)L2(H)...HOR complexes. When the temperature increases to ambient, the proton transfer and evolution of molecular hydrogen occur, affording the final products: organyloxy derivatives W(OR)(CO)2(NO)L2. The study of the kinetics at 298 K found that the proton transfer is the rate-determining step. The rate constants k app are 2.2·10−5–6.3·10−4 s−1, and the free activation energies are ΔG ≠ 298K = 22–23 kcal mol−1. The rate constants depend on the proton-accepting properties of the hydride and the acidic properties of the OH-proton donor and increase in the same order as the enthalpy of hydrogen bond formation.
- Добавил в систему: Шубина Елена Соломоновна