Halide Abstraction Competes with Oxidative Addition in the Reactions of Aryl Halides with [Ni(PMe<inf>n</inf>Ph<inf>(3−n)</inf>)<inf>4</inf>]

Ignacio Funes-Ardoiz, David J. Nelson, Feliu Maseras

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38 Citations (Scopus)


© 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. Density functional theory (DFT) calculations have been used to study the oxidative addition of aryl halides to complexes of the type [Ni(PMenPh(3−n))4], revealing the crucial role of an open-shell singlet transition state for halide abstraction. The formation of NiI versus NiII has been rationalised through the study of three different pathways: (i) halide abstraction by [Ni(PMenPh(3−n))3], via an open-shell singlet transition state; (ii) SN2-type oxidative addition to [Ni(PMenPh(3−n))3], followed by phosphine dissociation; and (iii) oxidative addition to [Ni(PMenPh(3−n))2]. For the overall reaction between [Ni(PMe3)4], PhCl, and PhI, a microkinetic model was used to show that our results are consistent with the experimentally observed ratios of NiI and NiII when the PEt3 complex is used. Importantly, [Ni(PMenPh(3−n))2] complexes often have little, if any, role in oxidative addition reactions because they are relatively high in energy. The behaviour of [Ni(PR3)4] complexes in catalysis is therefore likely to differ considerably from those based on diphosphine ligands in which two coordinate Ni0 complexes are the key species undergoing oxidative addition.
Original languageEnglish
Pages (from-to)16728-16733
JournalChemistry - A European Journal
Issue number66
Publication statusPublished - 27 Nov 2017


  • density functional calculations
  • electron transfer
  • homogeneous catalysis
  • ligand effects
  • nickel


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