Impact of the Methylene Bridge Substitution in Chelating NHC‐Phosphine Mn(I) Catalyst for Ketone Hydrogenation - Archive ouverte HAL Accéder directement au contenu
Article Dans Une Revue Chemistry - A European Journal Année : 2024

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

Stéphanie Bastin
Carine Duhayon
Noël Lugan
  • Fonction : Auteur
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Résumé

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.
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Origine : Publication financée par une institution
Licence : CC BY - Paternité

Dates et versions

hal-04522874 , version 1 (27-03-2024)

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Ekaterina S Gulyaeva, Ruqaya Buhaibeh, Mohamed Boundor, Karim Azouzi, Jérémy Willot, et al.. Impact of the Methylene Bridge Substitution in Chelating NHC‐Phosphine Mn(I) Catalyst for Ketone Hydrogenation. Chemistry - A European Journal, inPress, pp.e202304201. ⟨10.1002/chem.202304201⟩. ⟨hal-04522874⟩
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