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Dihydrogen Bonding in Complex (PP3)RuH(eta(1)-BH4) Featuring Two Proton-Accepting Hydride Sites: Experimental and Theoretical Studiesстатья
Статья опубликована в высокорейтинговом журнале
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: 11 марта 2017 г.
- Авторы: Belkova Natalia V., Bakhmutova-Albert Ekaterina V., Gutsul Evgenii L., Bakhmutov Vladimir I., Golub Igor E., Filippov Oleg A., Epstein Lina M., Peruzzini Maurizio, Rossin Andrea, Zanobini Fabrizio, Shubinat Elena S.
- Журнал: Inorganic Chemistry
- Том: 53
- Номер: 2
- Год издания: 2014
- Издательство: American Chemical Society
- Местоположение издательства: United States
- Первая страница: 1080
- Последняя страница: 1090
- DOI: 10.1021/ic4026206
- Аннотация: Combining variable-temperature infrared and NMR spectroscopic studies with quantum-chemical calculations (density functional theory (DFT) and natural bond orbital) allowed us to address the problem of competition between MH (M = transition metal) and BH hydrogens as proton-accepting sites in dihydrogen bond (DHB) and to unravel the mechanism of proton transfer to complex (PP3)RuH(eta(1)-BH4) (1, PP3 = kappa(4)-P(CH2CH2PPh2)(3)). Interaction of complex 1 with CH3OH, fluorinated alcohols of variable acid strength [CH2FCH2OH, CF3CH2OH, (CF3)(2)CHOH (HFIP), (CF3)(3)COH], and CF3COOH leads to the medium-strength DHB complexes involving BH bonds (3-5 kcal/mol), whereas DHB complexes with RuH were not observed experimentally. The two proton-transfer pathways were considered in DFT/M06 calculations. The first one goes via more favorable bifurcate complexes to BHterm and high activation barriers (38.2 and 28.4 kcal/mol in case of HFIP) and leads directly to the thermodynamic product [(PP3)RuHeq(H-2)](+)[OR](-). The second pathway starts from the less-favorable complex with RuH ligand but shows a lower activation barrier (23.5 kcal/mol for HFIP) and eventually leads to the final product via the isomerization of intermediate [(PP3)RuHax(H-2)](+)[OR](-). The B-H-br, bond breaking is the common key step of all pathways investigated.
- Добавил в систему: Голуб Игорь Евгеньевич