Half‐Sandwich Manganese Complex Bearing Fused Oxazoline‐NHC Ligand: Conformational Analysis and Evaluation in Asymmetric Ketone Hydrosilylation - Archive ouverte HAL
Article Dans Une Revue European Journal of Inorganic Chemistry Année : 2023

Half‐Sandwich Manganese Complex Bearing Fused Oxazoline‐NHC Ligand: Conformational Analysis and Evaluation in Asymmetric Ketone Hydrosilylation

Résumé

The first manganese complex bearing a chiral N-heterocyclic carbene (NHC) ligand was prepared and studied by spectroscopic methods and X-ray diffraction. While IR spectroscopy revealed the existence of two isomers in solution with distinct νCO band patterns, DFT calculations indicated that these isomers correspond to rotamers around the Mn−NHC bond and their different spectroscopic properties were rationalized by the occurrence of attractive π(C=C)⋅⋅⋅π*(C≡O) or σ(C−H)⋅⋅⋅π*(C≡O) intramolecular interligand interactions. The evaluation of this complex in catalytic hydrosilylation of acetophenone using Ph2SiH2 under UV irradiation led to the formation of the corresponding (R)-alcohol with low enantioselectivity.
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Dates et versions

hal-04142519 , version 1 (27-06-2023)

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Matthieu Cavailles, Oleg Filippov, Vincent César, Noël Lugan, Dmitry Valyaev. Half‐Sandwich Manganese Complex Bearing Fused Oxazoline‐NHC Ligand: Conformational Analysis and Evaluation in Asymmetric Ketone Hydrosilylation. European Journal of Inorganic Chemistry, 2023, 26 (18), pp.e202300143. ⟨10.1002/ejic.202300143⟩. ⟨hal-04142519⟩
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