Impact of the Methylene Bridge Substitution in Chelating NHC-Phosphine Mn(I) Catalyst for Ketone Hydrogenation.

Autor: Gulyaeva ES; LCC-CNRS, Université de Toulouse, CNRS, UPS, 205 route de Narbonne, 31077, Toulouse Cedex 4, France.; A. N. Nesmeyanov Institute of Organoelement Compounds (INEOS), Russian Academy of Sciences, 28/1 Vavilov str., GSP-1, B-334, Moscow, 119334, Russia., Buhaibeh R; LCC-CNRS, Université de Toulouse, CNRS, UPS, 205 route de Narbonne, 31077, Toulouse Cedex 4, France., Boundor M; LCC-CNRS, Université de Toulouse, CNRS, UPS, 205 route de Narbonne, 31077, Toulouse Cedex 4, France., Azouzi K; LCC-CNRS, Université de Toulouse, CNRS, UPS, 205 route de Narbonne, 31077, Toulouse Cedex 4, France., Willot J; LCC-CNRS, Université de Toulouse, CNRS, UPS, 205 route de Narbonne, 31077, Toulouse Cedex 4, France., Bastin S; LCC-CNRS, Université de Toulouse, CNRS, UPS, 205 route de Narbonne, 31077, Toulouse Cedex 4, France., Duhayon C; LCC-CNRS, Université de Toulouse, CNRS, UPS, 205 route de Narbonne, 31077, Toulouse Cedex 4, France., Lugan N; LCC-CNRS, Université de Toulouse, CNRS, UPS, 205 route de Narbonne, 31077, Toulouse Cedex 4, France., Filippov OA; A. N. Nesmeyanov Institute of Organoelement Compounds (INEOS), Russian Academy of Sciences, 28/1 Vavilov str., GSP-1, B-334, Moscow, 119334, Russia., Sortais JB; LCC-CNRS, Université de Toulouse, CNRS, UPS, 205 route de Narbonne, 31077, Toulouse Cedex 4, France.; Institut Universitaire de France, 1 rue Descartes, 75231, Paris Cedex 5, France., Valyaev DA; LCC-CNRS, Université de Toulouse, CNRS, UPS, 205 route de Narbonne, 31077, Toulouse Cedex 4, France., Canac Y; LCC-CNRS, Université de Toulouse, CNRS, UPS, 205 route de Narbonne, 31077, Toulouse Cedex 4, France.
Jazyk: angličtina
Zdroj: Chemistry (Weinheim an der Bergstrasse, Germany) [Chemistry] 2024 Apr 16; Vol. 30 (22), pp. e202304201. Date of Electronic Publication: 2024 Feb 28.
DOI: 10.1002/chem.202304201
Abstrakt: Systematic modification of the chelating NHC-phosphine ligand (NHC = N-heterocyclic carbene) in highly efficient ketone hydrogenation Mn(I) catalyst fac-[(Ph 2 PCH 2 NHC)Mn(CO) 3 Br] has been performed and the catalytic activity of the resulting complexes was evaluated using acetophenone as a benchmark substrate. While the variation of phosphine and NHC moieties led to inferior results than for a parent system, the incorporation of a phenyl substituent into the ligand methylene bridge improved catalytic performance by ca. 3 times providing maximal TON values in the range of 15000-20000. Mechanistic investigation combining experimental and computational studies allowed to rationalize this beneficial effect as an enhanced stabilization of reaction intermediates including anionic hydride species fac-[(Ph 2 PC(Ph)NHC)Mn(CO) 3 H] - playing a crucial role in the hydrogenation process. These results highlight the interest of such carbon bridge substitution strategy being rarely employed in the design of chemically non-innocent ligands.
(© 2024 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)
Databáze: MEDLINE
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