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)

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