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

Sonia Bajo, Gillian Laidlaw, Alan R. Kennedy, Stephen Sproules, David J. Nelson

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67 Citations (Scopus)
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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.
Original languageEnglish
Pages (from-to)1662-1672
Number of pages11
JournalOrganometallics
Volume36
Issue number8
Early online date6 Apr 2017
DOIs
Publication statusPublished - 24 Apr 2017

Keywords

  • nickel
  • oxidative addition
  • mechanistic studies
  • kinetics
  • cross coupling

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