title: Highly Active Nickel Catalysts for C-H Functionalization Identified through Analysis of Off-Cycle Intermediates.
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.
authors.affiliation: Department of Chemistry, University of Michigan, 930 North University Avenue, Ann Arbor, Michigan 48019-1055, United States.
authors.forename: Alex J
authors.initials: AJ
authors.lastname: Nett
authors.affiliation: Department of Chemistry, University of Michigan, 930 North University Avenue, Ann Arbor, Michigan 48019-1055, United States.
authors.forename: Wanxiang
authors.initials: W
authors.lastname: Zhao
authors.affiliation: Department of Chemistry, University of Michigan, 930 North University Avenue, Ann Arbor, Michigan 48019-1055, United States.
authors.forename: Paul M
authors.initials: PM
authors.lastname: Zimmerman
authors.affiliation: Department of Chemistry, University of Michigan, 930 North University Avenue, Ann Arbor, Michigan 48019-1055, United States.
authors.forename: John
authors.initials: J
authors.lastname: Montgomery