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In-depth NMR and IR study of the proton transfer equilibrium between [{(MeC(CH2PPh2)(3)}Ru(CO)H-2] and hexafluoroisopropanolстатья
Информация о цитировании статьи получена из
Web of Science,
Scopus
Дата последнего поиска статьи во внешних источниках: 24 марта 2017 г.
- Авторы: Bakhmutov V.I., Bakhmutova E.V., Belkova N.V., Bianchini C., Epstein L.M., Masi D., Peruzzini M., Shubina E.S., Vorontsov E.V., Zanobini F.
- Журнал: CANADIAN JOURNAL OF CHEMISTRY-REVUE CANADIENNE DE CHIMIE
- Том: 79
- Номер: 5-6
- Год издания: 2001
- Первая страница: 479
- Последняя страница: 489
- DOI: 10.1139/cjc-79-5-6-479
- Аннотация: The (carbonyl)dihydride complex [(triphos)Ru(CO)H-2] (2) has been synthesized by reaction of the ruthenate [(triphos)RuH3]K (triphos = MeC(CH2PPh2)(3)) with ethanol saturated with CO. A single crystal X-ray analysis and IR and NMR experiments have shown that 2 adopts in both the solid state and solution an octahedral coordination geometry with a facial triphos ligand, two cis terminal hydrides, and a terminal carbonyl. The reaction of hexafluoro-2-propanol (HFIP) with 2 has been studied in CH2Cl2 solution by IR and NMR spectroscopy. The proton donor interacts with a terminal hydride of 2 forming a rather strong hydrogen bond. The resulting H-bonded adduct [{(triphos)Ru(CO)(H)H}. . . {HOCH(CF3)(2)}] (2a) has fully been characterized by in situ NMR and IR techniques. Compound 2a is in equilibrium with the nonclassical eta(2)-H-2 complex [(triphos)Ru(CO)H(H-2)](+) (2b), which can independently be prepared by protonation of 2 with a strong protic acid at low temperature. Unequivocal characterization of the dihydrogen complex (2b) has been achieved by a multifaceted spectroscopic investigation (T>(obs)(1min) = 0.005 s (200 MHz), J(H,D) approximate to 30 Hz, DQCC = 78.3 kHz). A combined IR and NMR study of the proton transfer reaction involving 2 and HFIP in CH2Cl2 to give, first, the H-bonded adduct (2a) and, then, the dihydrogen complex (2b) has demonstrated that all these species are in equilibrium in the temperature range from 190 to 260 K. The thermodynamic parameters for the formation of 2a have independently been determined by NMR and IR methods, while those for the formation of 2b have been obtained by IR spectroscopy. An energetic profile for the reaction sequence 2 right arrow 2a right arrow 2b is proposed and discussed.
- Добавил в систему: Шубина Елена Соломоновна