|
ИСТИНА |
Войти в систему Регистрация |
ФНКЦ РР |
||
Proton transfer to CpRuH(CO)(PCy3) studied by low-temperature IR and NMR spectroscopyстатья
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: 24 марта 2017 г.
- Авторы: Belkova N.V., Ionidis A.V., Epstein L.M., Shubina E.S., Gruendemann S., Golubev N.S., Limbach H.H.
- Журнал: European Journal of Inorganic Chemistry
- Номер: 7
- Год издания: 2001
- Издательство: John Wiley & Sons Ltd.
- Местоположение издательства: United Kingdom
- Первая страница: 1753
- Последняя страница: 1761
- DOI: 10.1002/1099-0682(200107)2001:7
- Аннотация: The interaction of the ruthenium hydride complex RuH = CpRuH(CO)(PCy3) (1) with various proton donors AH = CF3CH2OH (2a), (CF3)(2)CHOH (2b), (CF3)(3)COH (2c), CF3COOH (2d), and HBF4 (2e) has been studied by variable-temperature IR spectroscopy using hexane and CH2Cl2 as solvents of different polarity. A low-temperature NMR study of the interaction of 1 with 2e was performed using [D-8]methylcyclohexane, CD2Cl2, and a liquefied mixture of CDF2Cl/CDF3 (2:1). The first stage of the proton transfer process was found to be the formation of hydrogen-bonded complexes of the type RuH PIA. The hydrogen bonds in these complexes are of medium strength (-DeltaH degrees = 5.3-7.6 kcal mol(-1)). The second stage is the slow conversion of the H-complex to a dihydrogen complex to which a hydrogen-bonded ion-pair structure [Ru(eta (2)-H-2)](+)...A(-) was assigned. The kinetics of this unusually Slow proton transfer reaction was monitored in the case of 2c at 200 K in CH2Cl2. Fast protonation of 1 by 2d leads additionally to a species assigned as the free cationic complex [RU(eta (2)-H-2)](+), whose formation is driven by the formation of the homoconjugated anionic complex [AHA](-). At temperatures above 220 K both the hydrogen-bonded ion pair and the free cationic complex easily release dihydrogen, producing RuA.
- Добавил в систему: Шубина Елена Соломоновна