Oxidative addition of aryl electrophiles to a prototypical nickel(0) complex : mechanism and structure/reactivity relationships
Bajo, Sonia and Laidlaw, Gillian and Kennedy, Alan R. and Sproules, Stephen and Nelson, David J. (2017) Oxidative addition of aryl electrophiles to a prototypical nickel(0) complex : mechanism and structure/reactivity relationships. Organometallics, 36 (8). pp. 1662-1672. ISSN 0276-7333 (https://doi.org/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.
ORCID iDs
Bajo, Sonia ORCID: https://orcid.org/0000-0003-4803-566X, Laidlaw, Gillian, Kennedy, Alan R. ORCID: https://orcid.org/0000-0003-3652-6015, Sproules, Stephen and Nelson, David J. ORCID: https://orcid.org/0000-0002-9461-5182;-
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Item type: Article ID code: 60367 Dates: DateEvent24 April 2017Published6 April 2017Published Online29 March 2017AcceptedNotes: Copyright © 2017 American Chemical Society. Bajo, S., Laidlaw, G., Kennedy, A. R., Sproules, S., & Nelson, D. J. (2017). Oxidative addition of aryl electrophiles to a prototypical nickel(0) complex: mechanism and structure/reactivity relationships. Organometallics, 1-33. Article accepted for publication by ACS. Subjects: Science > Chemistry Department: Faculty of Science > Pure and Applied Chemistry Depositing user: Pure Administrator Date deposited: 30 Mar 2017 09:30 Last modified: 29 Sep 2024 08:14 Related URLs: URI: https://strathprints.strath.ac.uk/id/eprint/60367