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Интеллектуальная Система Тематического Исследования НАукометрических данных |
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Solvent-Dependent Dihydrogen/Dihydride Stability for [Mo(CO)(Cp*)H-2(PMe3)(2)](+)[BF4](-) Determined by Multiple Solvent center dot center dot center dot Anion center dot center dot center dot Cation Non-Covalent Interactionsстатья
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 марта 2017 г.
- Авторы: Dub Pavel A., Belkova Natalia V., Filippov Oleg A., Daran Jean-Claude, Epstein Lina M., Lledos Agusti, Shubina Elena S., Poli Rinaldo
- Журнал: Chemistry - A European Journal
- Том: 16
- Номер: 1
- Год издания: 2010
- Издательство: John Wiley & Sons Ltd.
- Местоположение издательства: United Kingdom
- Первая страница: 189
- Последняя страница: 201
- DOI: 10.1002/chem.200901613
- Аннотация: Low-temperature (200 K) protonation of [Mo(CO)(Cp*)H(PMe3)(2)] (1) by Et2O center dot HBF4 gives a different result depending on a subtle solvent change: The dihydrogen complex [Mo(Co)(Cp*)(eta(2)-H-2)(PMe3)(2)](+) (2) is obtained in THE whereas the tautomeric classical dihydride [Mo(CO)(Cp*)(H)(2)(PMe3)(2)](+) (3) is the only observable product in dichloromethane. Both products were fully characterised (nu(CO) IR; H-1, P-31, C-13 NMR spectroscopies) at low temperature; they lose H-2 upon warming to 230 K at approximately the same rate (ca. 10(-3)s(-1)), with no detection of the non-classical form in CD2Cl2, to generate [Mo(CO)(Cp*)(FBF3)(PMe3)(2)] (4). The latter also slowly decomposes at ambient temperature. One of the decomposition products was crystallised and identified by X-ray crystallography as [Mo(CO)(Cp*)(FH center dot center dot center dot FBF3)(PMe3)(2)] (5), which features a neutral HF ligand coordinated to the transition metal through the F atom and to the BF4- anion through a hydrogen bond. The reason for the switch in relative stability between 2 and 3 was probed by DFT calculations based on the B3LYP and M05-2X functionals, with inclusion of anion and solvent effects by the conductor-like polarisable continuum model and by explicit consideration of the solvent molecules. Calculations at the MP4(SDQ) and CCSD(T) levels were also carried out for calibration. The calculations reveal the key role of non-covalent anion-solvent interactions, which modulate the anion-cation interaction ultimately altering the energetic balance between the two isomeric forms.
- Добавил в систему: Шубина Елена Соломоновна