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 |
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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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