Oxidative addition of aryl electrophiles to a prototypical nickel(0) complex: mechanism and structure/reactivity relationships

Bajo, S., Laidlaw, G., Kennedy, A. R. and Sproules, S. (2017) Oxidative addition of aryl electrophiles to a prototypical nickel(0) complex: mechanism and structure/reactivity relationships. Organometallics, 36(8), pp. 1662-1672. (doi:10.1021/acs.organomet.7b00208)

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Abstract

Detailed kinetic studies of the reaction of a model Ni0 complex with a range of aryl electrophiles have been conducted. The reactions proceed via a fast ligand exchange pre-equilibrium, followed by oxidative addition to produce either [NiIX(dppf)] (and biaryl) or [NiII(Ar)X(dppf)]; the ortho substituent of the aryl halide determines selectivity between these possibilities. A reactivity scale is presented in which a range of substrates is quantitatively ranked in order of the rate at which they undergo oxidative addition. The rate of oxidative addition is loosely correlated to conversion in prototypical cross-coupling reactions. Substrates that lead to NiI products in kinetic experiments produce more homocoupling products under catalytic conditions.

Item Type:Articles
Status:Published
Refereed:Yes
Glasgow Author(s) Enlighten ID:Sproules, Dr Stephen
Authors: Bajo, S., Laidlaw, G., Kennedy, A. R., and Sproules, S.
College/School:College of Science and Engineering > School of Chemistry
Journal Name:Organometallics
Publisher:American Chemical Society
ISSN:0276-7333
ISSN (Online):1520-6041
Published Online:06 April 2017
Copyright Holders:Copyright © 2017 The Authors
First Published:First published in Organometallics 36(8):1662–1672
Publisher Policy:Reproduced under a Creative Commons License

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