Phosphine-NHC Manganese Hydrogenation Catalyst Exhibiting a Non-Classical Metal-Ligand Cooperative H2 Activation Mode

Авторы: Buhaibeh Ruqaya, Filippov Oleg A., Bruneau-Voisine Antoine, Willot Jérémy, Duhayon Carine, Valyaev Dmitry A., Lugan Noël, Canac Yves, Sortais Jean-Baptiste
Журнал: Angewandte Chemie - International Edition
Том: 58
Номер: 20
Год издания: 2019
Издательство: John Wiley & Sons Ltd.
Местоположение издательства: United Kingdom
Первая страница: 6727
Последняя страница: 6731
DOI: 10.1002/anie.201901169
Аннотация: Deprotonation of the MnI NHC‐phosphine complex fac‐[MnBr(CO)3(κ2P,C‐Ph2PCH2NHC)] (2) under a H2 atmosphere readily gives the hydride fac‐[MnH(CO)3(κ2P,C‐Ph2PCH2NHC)] (3) via the intermediacy of the highly reactive 18‐e NHC‐phosphinomethanide complex fac‐[Mn(CO)3(κ3P,C,C‐Ph2PCHNHC)] (6 a). DFT calculations revealed that the preferred reaction mechanism involves the unsaturated 16‐e mangana‐substituted phosphonium ylide complex fac‐[Mn(CO)3(κ2P,C‐Ph2P=CHNHC)] (6 b) as key intermediate able to activate H2 via a non‐classical mode of metal‐ligand cooperation implying a formal λ5‐P–λ3‐P phosphorus valence change. Complex 2 is shown to be one of the most efficient pre‐catalysts for ketone hydrogenation in the MnI series reported to date (TON up to 6200).
Добавил в систему: Filippov Oleg Andreevich

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