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Updated: Apr 11, 2026

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Highly Active Nickel Catalysts for C-H Functionalization Identified through Analysis of Off-Cycle Intermediates
Alex J Nett1, Wanxiang Zhao1, Paul M Zimmerman1
1Department of Chemistry, University of Michigan, 930 North University Avenue, Ann Arbor, Michigan 48019-1055, United States.
Abstract:
An inhibitory role of 1,5-cyclooctadiene (COD) in nickel-catalyzed C-H functionalization processes was identified and studied. The bound COD participates in C-H activation by capturing the hydride, leading to a stable off-cycle π-allyl complex that greatly diminished overall catalytic efficiency. Computational studies elucidated the origin of the effect and enabled identification of a 1,5-hexadiene-derived pre-catalyst that avoids the off-cycle intermediate and provides catalytic efficiencies that are superior to those of catalysts derived from Ni(COD)2.
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