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Highly Active Iridium Catalysts for Alkane Dehydrogenation. Synthesis and Properties of Iridium Bis(phosphine) Pincer Complexes Based on Ferrocene and Ruthenoceneстатья
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: 28 июля 2014 г.
- Авторы: Kuklin S.A., Sheloumov A.M., Dolgushin F.M., Ezernitskaya M.G., Peregudov A.S., Petrovskii P.V., Koridze A.A.
- Журнал: Organometallics
- Том: 25
- Год издания: 2006
- Издательство: American Chemical Society
- Местоположение издательства: United States
- Первая страница: 5466
- Последняя страница: 5476
- DOI: 10.1021/om060715w
- Аннотация: Novel bis(phosphine) pincer complexes of iridium based on ferrocene and ruthenocene have been synthesized. The reaction of 1,3-bis((di-tert-butylphosphino)methyl)metallocenes [t-BuP,CH,PM] (M = Fe, 10; M = Ru, 13) with [Ir(COE)2Cl]2 in refluxing toluene leads to the corresponding chloro-hydrido pincer complexes as a mixture of H-endo- (M = Fe, 11; M = Ru, 14) and H-exo-IrH(Cl)[t-BuP,C,PM] (M = Fe, 12; M = Ru, 15) isomers. Treatment of compounds 11, 12 and 14, 15 with NaH in hot cyclooctane generates corresponding dihydrido complexes IrH2[t-BuP,C,PM] (M = Fe, 6; M = Ru, 7). Reactivity of the chelated iridium atom in hydrido-iridium pincer complexes and oxidation centered at the iron atom of ferrocene-based pincer complexes were studied. Complexes H-exo-IrH(Cl)(CO)[t-BuP,C,PFe] (20), Ir(CO)[t-BuP,C,PFe] (21), and Ir(CO)[2,6-(tBu2PO)2C6H3] (30) were characterized by X-ray crystallography. On the basis of vCO values for carbonyl iridium derivatives, electronic characteristics of the corresponding fragments {Ir[t-BuP,C,PM]}n (n = 0, +1) were elucidated. Complexes 6 and 7 reveal unprecedented catalytic activity in cyclooctane dehydrogenation in the presence of tert-butylethylene as a hydrogen acceptor: turnover numbers 3300, 2571, and 1843 were obtained for 6, 7, and the known complex IrH2[2,6-(tBu2-PO)2C6H3] (4c), respectively, at 180 °C for 8 h. The high catalytic activity for 6 and 7 and the difference in the catalytic activity of these “isostructural” complexes are discussed in terms of steric and electronic effects.
- Добавил в систему: Куклин Сергей Александрович
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