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

Autor: Matthieu Cavailles, Oleg A. Filippov, Vincent César, Noël Lugan, Dmitry A. Valyaev
Přispěvatelé: Laboratoire de chimie de coordination (LCC), Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS), A. N. Nesmeyanov Institute of Organoelement Compounds (INEOS), Russian Academy of Sciences [Moscow] (RAS), Centre National de la Recherche Scientifique (CNRS), Ministry of Science and Higher Education of the Russian Federation
Rok vydání: 2023
Předmět:
Zdroj: European Journal of Inorganic Chemistry
European Journal of Inorganic Chemistry, 2023, 26 (18), pp.e202300143. ⟨10.1002/ejic.202300143⟩
ISSN: 1099-0682
1434-1948
Popis: International audience; 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.
Databáze: OpenAIRE
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