A New Mode of Operation of Pd-NHC Systems Studied in a Catalytic Mizoroki–Heck Reaction

Astakhov, A.V.; Khazipov, O.V.; Chernenko, A.Y.; Pasyukov, D.V.; Kashin, A.S.; Gordeev, E.G.; Khrustalev, V.N.; Chernyshev, V.M.; Ananikov, V.P.

Авторы: Astakhov Alexander V., Khazipov Oleg V., Chernenko Andrey Yu, Pasyukov Dmitry V., Kashin Alexey S., Gordeev Evgeniy G., Khrustalev Victor N., Chernyshev Victor M., Ananikov Valentine P.
Журнал: Organometallics
Том: 36
Номер: 10
Год издания: 2017
Издательство: American Chemical Society
Местоположение издательства: United States
Первая страница: 1981
Последняя страница: 1992
DOI: 10.1021/acs.organomet.7b00184
Аннотация: Metal complexes bearing N-heterocyclic carbene (NHC) ligands are typically considered the system of choice for homogeneous catalysis with well-defined molecular active species due to their stable metal–ligand framework. A detailed study involving 19 different Pd-NHC complexes with imidazolium, benzimidazolium, and triazolium ligands has been carried out in the present work and revealed a new mode of operation of metal-NHC systems. The catalytic activity of the studied Pd-NHC systems is predominantly determined by the cleavage of the metal–NHC bond, while the catalyst performance is strongly affected by the stabilization of in situ formed metal clusters. In the present study, the formation of Pd nanoparticles was observed from a broad range of metal complexes with NHC ligands under standard Mizoroki–Heck reaction conditions. A mechanistic analysis revealed two different pathways to connect Pd-NHC complexes to “cocktail”-type catalysis: (i) reductive elimination from a Pd(II) intermediate and the release of NHC-containing byproducts and (ii) dissociation of NHC ligands from Pd intermediates. Metal-NHC systems are ubiquitously applied in modern organic synthesis and catalysis, while the new mode of operation revealed in the present study guides catalyst design and opens a variety of novel opportunities. As shown by experimental studies and theoretical calculations, metal clusters and nanoparticles can be readily formed from M-NHC complexes after formation of new M–C or M–H bonds followed by C–NHC or H–NHC coupling. Thus, a combination of a classical molecular mode of operation and a novel cocktail-type mode of operation, described in the present study, may be anticipated as an intrinsic feature of M-NHC catalytic systems.
Добавил в систему: Анаников Валентин Павлович

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A New Mode of Operation of Pd-NHC Systems Studied in a Catalytic Mizoroki–Heck Reactionстатья Исследовательская статья