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Dimerization Mechanism of Bis(triphenylphosphine)copper(I) Tetrahydroborate: Proton Transfer via a Dihydrogen Bondстатья
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: 18 июля 2013 г.
- Авторы: Golub Igor E., Filippov Oleg A., Gutsul Evgenii I., Belkova Natalia V., Epstein Lina M., Rossin Andrea, Peruzzini Maurizio, Shubina Elena S.
- Журнал: Inorganic Chemistry
- Том: 51
- Номер: 12
- Год издания: 2012
- Издательство: American Chemical Society
- Местоположение издательства: United States
- Первая страница: 6486
- Последняя страница: 6497
- DOI: 10.1021/ic202598c
- Аннотация: The mechanism of transition-metal tetrahydroborate dimerization was established for the first time on the example of (Ph3P)2Cu(η2-BH4) interaction with different proton donors [MeOH, CH2FCH2OH, CF3CH2OH, (CF3)2CHOH, (CF3)3CHOH, p-NO2C6H4OH, p-NO2C6H4N═NC6H4OH, p-NO2C6H4NH2] using the combination of experimental (IR, 190–300 K) and quantum-chemical (DFT/M06) methods. The formation of dihydrogen-bonded complexes as the first reaction step was established experimentally. Their structural, electronic, energetic, and spectroscopic features were thoroughly analyzed by means of quantum-chemical calculations. Bifurcate complexes involving both bridging and terminal hydride hydrogen atoms become thermodynamically preferred for strong proton donors. Their formation was found to be a prerequisite for the subsequent proton transfer and dimerization to occur. Reaction kinetics was studied at variable temperature, showing that proton transfer is the rate-determining step. This result is in agreement with the computed potential energy profile of (Ph3P)2Cu(η2-BH4) dimerization, yielding [{(Ph3P)2Cu}2(μ,η4-BH4)]+.
- Добавил в систему: Голуб Игорь Евгеньевич
Прикрепленные файлы
| № | Имя | Описание | Имя файла | Размер | Добавлен |
|---|---|---|---|---|---|
| 1. | Полный текст | Article | Inorg_Chem_2012.pdf | 2,6 МБ | 20 января 2013 [Thunderbolt] |
| 2. | Результаты экспериментов | Supportin Information | ic202598c_si_001.pdf | 2,7 МБ | 20 января 2013 [Thunderbolt] |