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

[img]
Preview
 Text (Funes-Ardoiz-CEJ2017-Halide-abstraction-competes-with-oxidative-addition-in-the-reactions)
Funes_Ardoiz_CEJ2017_Halide_abstraction_competes_with_oxidative_addition_in_the_reactions.pdf
Final Published Version
License: Creative Commons Attribution 4.0 logo
Download (1MB)| Preview

    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.

    Creators(s): Funes-Ardoiz, Ignacio, Nelson, David J. ORCID logoORCID: https://orcid.org/0000-0002-9461-5182 and Maseras, Feliu;
    Item type:Article
    ID code:62120
    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:18 Sep 2020 04:52
    Related URLs:
    URI:https://strathprints.strath.ac.uk/id/eprint/62120
    Export data:
    CORE (COnnecting REpositories)