Halide abstraction competes with oxidative addition in the reactions of aryl halides with [Ni(PMenPh(3-n))4]

Funes-Ardoiz, Ignacio and Nelson, David J. and Maseras, Feliu (2017) Halide abstraction competes with oxidative addition in the reactions of aryl halides with [Ni(PMenPh(3-n))4]. Chemistry - A European Journal, 23 (66). pp. 16728-16733. ISSN 0947-6539

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    Abstract

    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 case of [Ni(PMe3)4], a microkinetic model was used to show that these data are consistent with the experimentally-observed ratios of NiI and NiII. Importantly, [Ni(PMenPh(3-n))2] complexes often have little if any role in the oxidative addition reaction 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.

    ORCID iDs

    Funes-Ardoiz, Ignacio, Nelson, David J. ORCID logoORCID: https://orcid.org/0000-0002-9461-5182 and Maseras, Feliu;
    • Item type:Article
      ID code:62120
      Dates:
      Date
      Event
      27 November 2017
      Published
      20 November 2017
      Published Online
      19 October 2017
      Accepted
      Keywords:density fuctional calculations, homogenous catalysis, nickel, electron transfer, ligand effects, Chemistry, Chemistry(all)
      Subjects:Science > Chemistry
      Department:Faculty of Science > Pure and Applied Chemistry
      Depositing user: Pure Administrator
      Date deposited:23 Oct 2017 11:10
      Last modified:23 Sep 2021 06:24
      Related URLs:
      URI:https://strathprints.strath.ac.uk/id/eprint/62120
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