TY - DATA T1 - Highly Active Nickel Catalysts for C–H Functionalization Identified through Analysis of Off-Cycle Intermediates PY - 2015/06/24 AU - Alex J. Nett AU - Wanxiang Zhao AU - Paul M. Zimmerman AU - John Montgomery UR - https://acs.figshare.com/articles/journal_contribution/Highly_Active_Nickel_Catalysts_for_C_H_Functionalization_Identified_through_Analysis_of_Off_Cycle_Intermediates/2204596 DO - 10.1021/jacs.5b04548.s001 L4 - https://ndownloader.figshare.com/files/3839152 KW - IntermediatesAn KW - origin KW - hydride KW - Functionalization KW - cyclooctadiene KW - role KW - functionalization KW - identification KW - Active Nickel Catalysts KW - Computational studies KW - allyl KW - activation KW - Identified KW - Analysis KW - catalyst KW - efficiency N2 - 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. ER -