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Investigation of the [Cp*Mo(PMe3)(3)H](n+) (n=0, 1) Redox Pair: Dynamic Processes on Very Different Time Scalesстатья
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: Baya Miguel, Dub Pavel A., Houghton Jennifer, Daran Jean-Claude, Belkova Natalia V., Shubina Elena S., Epstein Lina M., Lledos Agusti, Poli Rinaldo
- Журнал: Inorganic Chemistry
- Том: 48
- Номер: 1
- Год издания: 2009
- Издательство: American Chemical Society
- Местоположение издательства: United States
- Первая страница: 209
- Последняя страница: 220
- DOI: 10.1021/ic801676n
- Аннотация: The compound [CP*MO(PMe3)(3)H] (1) is reversibly oxidized at E-1/2 = -1.40 V vs ferrocene in MeCN. Its oxidation with Cp2FePF6 yields thermally stable [Cp*Mo(PMe3)(3)H]PF6 (2), which has been isolated and characterized by IR and EPR spectroscopy and by single-crystal X-ray diffraction. The H-1 and P-31 NMR spectra of 1 show two types of PMe3 ligands in a 1:2 ratio at low temperature, but only one average signal at room temperature, with activation parameters of Delta H-double dagger = 11.7(3) kcal mol(-1) and Delta S-double dagger = -3(1) eu for the exchange process. Although only one species is evidenced by NMR for 1 and by EPR for 2, the solution IR spectra of each complex show two bands in the nu(Mo-H) region (1, major at 1794 cm(-1) and minor at ca. 1730 cm(-1); 2, ca. 1800 and 1770 cm(-1) with approximately equal intensity), the position and relative intensity being little dependent on the solvent. A thorough DFT investigation suggests that these are different rotamers involving different relative orientations of the Cp* ring and the PMe3 ligands in these complexes. This ring rotation process is very rapid on the NMR and EPR time scale but slow on the IR time scale. The X-ray data and the theoretical calculations suggest the presence of weak Mo-H center dot center dot center dot F interactions in compound 2. The possibility of PMe3 dissociation, as well as other intramolecular rearrangements, for 1 and 2 is excluded by experimental and computational studies. Protonation of 1 yields [Cp*Mo(PMe3)(3)H-2](+) (3), which also reveals a dynamic process interconverting the two inequivalent H ligands and the three PMe3 ligands (two sets in a 1:2 ratio in the frozen structure) on the NMR time scale (activation parameters of Delta H double dagger = 9.3(1) kcal/mol and Delta S-double dagger = -4.1(4) eu). A DFT study suggests that this exchange process occurs via a low-energy symmetric dihydride intermediate and not through a dihydrogen complex.
- Добавил в систему: Шубина Елена Соломоновна