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Imine Metathesis by Silica-Supported Catalysts Using the Methodology of Surface Organometallic Chemistry
Published on: October 18, 2019
Imido-hydrido complexes of Mo(IV): catalysis and mechanistic aspects of hydroboration reactions
Andrey Y Khalimon1, Philip M Farha2, Georgii I Nikonov2
1Department of Chemistry, Brock University, 500 Glenridge Ave., St. Catharines, ON L2S 3A1, Canada. gnikonov@brocku.ca and Department of Chemistry, School of Science and Technology, Nazarbayev University, 53 Kabanbay Batyr Ave., Astana 010000, Kazakhstan. andrey.khalimon@nu.edu.kz.
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).
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