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Updated: Feb 25, 2026

Imine Metathesis by Silica-Supported Catalysts Using the Methodology of Surface Organometallic Chemistry
Published on: October 18, 2019
Heterolytic H-H and H-B Bond Cleavage Reactions of {(IPr)Ni(μ-S)}2
Frank Olechnowicz1, Gregory L Hillhouse1, Thomas R Cundari2
1Department of Chemistry, The University of Chicago , 5735 S. Ellis Avenue, Chicago, Illinois 60637, United States.
Abstract:
Kinetic and DFT computational studies reveal that the reaction of {(IPr)Ni(μ-S)}2 (1, IPr = 1,3-bis(2,6-diisopropyl-phenyl)imidazolin-2-ylidene) with dihydrogen to produce {(IPr)Ni(μ-SH)}2 (2) proceeds by rate-limiting heterolytic addition of H2 across a Ni-S bond of intact dinuclear 1, followed by cis/trans isomerization at Ni and subsequent H migration from Ni to S, to produce the bis-hydrosulfide product 2. Complex 1 reacts in a similar manner with pinacolborane to produce {(IPr)Ni}2(μ-SH)(μ-SBPin) (3), showing that heterolytic activation by this nickel μ-sulfide complex can be generalized to other H-E bonds.
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