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Phosphine-NHC Manganese Hydrogenation Catalyst Exhibiting a Non-Classical Metal-Ligand Cooperative H Activation Mode

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  • Additional Information
    • Contributors:
      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 - CNRS Chimie (INC-CNRS)-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); Institut des Sciences Chimiques de Rennes (ISCR); Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes); Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie - CNRS Chimie (INC-CNRS)-Centre National de la Recherche Scientifique (CNRS); Institut universitaire de France (IUF); Ministère de l'Education nationale, de l’Enseignement supérieur et de la Recherche (M.E.N.E.S.R.); Centre National de la Recherche (CNRS); Institut Universitaire de France (IUF); Embassy of Yemen in Paris
    • Publication Information:
      HAL CCSD
      Wiley-VCH Verlag
    • Publication Date:
      2019
    • Collection:
      Université de Rennes 1: Publications scientifiques (HAL)
    • Abstract:
      International audience ; Deprotonation of the Mn NHC-phosphine complex fac-[MnBr(CO) (κ P,C-Ph PCH NHC)] (2) under a H atmosphere readily gives the hydride fac-[MnH(CO) (κ P,C-Ph PCH NHC)] (3) via the intermediacy of the highly reactive 18-e NHC-phosphinomethanide complex fac-[Mn(CO) (κ P,C,C-Ph PCHNHC)] (6 a). DFT calculations revealed that the preferred reaction mechanism involves the unsaturated 16-e mangana-substituted phosphonium ylide complex fac-[Mn(CO) (κ P,C-Ph P=CHNHC)] (6 b) as key intermediate able to activate H via a non-classical mode of metal-ligand cooperation implying a formal λ -P-λ -P phosphorus valence change. Complex 2 is shown to be one of the most efficient pre-catalysts for ketone hydrogenation in the Mn series reported to date (TON up to 6200).
    • Relation:
      info:eu-repo/semantics/altIdentifier/pmid/30860308; PUBMED: 30860308
    • Accession Number:
      10.1002/anie.201901169
    • Online Access:
      https://univ-rennes.hal.science/hal-02120809
      https://univ-rennes.hal.science/hal-02120809v1/document
      https://univ-rennes.hal.science/hal-02120809v1/file/Buhaibeh_et_al-Phosphine-NHC_Manganese_Hydrogenation_Catalyst_Exhibiting_a_Non-Classical.pdf
      https://doi.org/10.1002/anie.201901169
    • Rights:
      info:eu-repo/semantics/OpenAccess
    • Accession Number:
      edsbas.DCAFE6C