Imido–hydrido complexes of Mo( iv ): catalysis and mechanistic aspects of hydroboration reactions

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

2015

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DOI 10.1039/c5dt02945g
Data confidence 85 high
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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)(N[double bond, length as m-dash]CHR)(PMe3)2; whereas for complex 2 stoichiometric reactions suggest initial addition of HBCat to form the agostic complex Mo(H)2(PMe3)3(η(3)-NAr-HBcat) (16).