Imido-hydrido complexes of Mo(IV): Catalysis and mechanistic aspects of hydroboration reactions

Andrey Y. Khalimon, Philip M. Farha, Georgii I. Nikonov

    Research output: Contribution to journalArticle

    20 Citations (Scopus)

    Abstract

    Imido-hydrido complexes (ArN)Mo(H)(Cl)(PMe3)3 (1) and (ArN)Mo(H)2(PMe3)3 (2) (Ar = 2,6-diisopropylphenyl) catalyse a variety of hydroboration reactions, including the rare examples of addition of HBCat to nitriles to form bis(borylated) amines RCH2N(BCat)2. Stoichiometric reactivity of complexes 1 and 2 with nitriles and HBCat suggest that catalytic reactions proceed via a series of agostic borylamido and borylamino complexes. For complex 1, catalysis starts with addition of nitriles across the Mo-H bond to give (ArN)Mo(Cl)(NCHR)(PMe3)2; whereas for complex 2 stoichiometric reactions suggest initial addition of HBCat to form the agostic complex Mo(H)2(PMe3)33-NAr-HBcat) (16).

    Original languageEnglish
    Pages (from-to)18945-18956
    Number of pages12
    JournalDalton Transactions
    Volume44
    Issue number43
    DOIs
    Publication statusPublished - 2015

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    Nitriles
    Catalysis
    Amines

    ASJC Scopus subject areas

    • Inorganic Chemistry

    Cite this

    Imido-hydrido complexes of Mo(IV) : Catalysis and mechanistic aspects of hydroboration reactions. / Khalimon, Andrey Y.; Farha, Philip M.; Nikonov, Georgii I.

    In: Dalton Transactions, Vol. 44, No. 43, 2015, p. 18945-18956.

    Research output: Contribution to journalArticle

    Khalimon, Andrey Y. ; Farha, Philip M. ; Nikonov, Georgii I. / Imido-hydrido complexes of Mo(IV) : Catalysis and mechanistic aspects of hydroboration reactions. In: Dalton Transactions. 2015 ; Vol. 44, No. 43. pp. 18945-18956.
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    abstract = "Imido-hydrido complexes (ArN)Mo(H)(Cl)(PMe3)3 (1) and (ArN)Mo(H)2(PMe3)3 (2) (Ar = 2,6-diisopropylphenyl) catalyse a variety of hydroboration reactions, including the rare examples of addition of HBCat to nitriles to form bis(borylated) amines RCH2N(BCat)2. Stoichiometric reactivity of complexes 1 and 2 with nitriles and HBCat suggest that catalytic reactions proceed via a series of agostic borylamido and borylamino complexes. For complex 1, catalysis starts with addition of nitriles across the Mo-H bond to give (ArN)Mo(Cl)(NCHR)(PMe3)2; whereas for complex 2 stoichiometric reactions suggest initial addition of HBCat to form the agostic complex Mo(H)2(PMe3)3(η3-NAr-HBcat) (16).",
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