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 (https://doi.org/10.1002/chem.201702331)
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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.
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Item type: Article ID code: 62120 Dates: DateEvent27 November 2017Published20 November 2017Published Online19 October 2017AcceptedSubjects: Science > Chemistry Department: Faculty of Science > Pure and Applied Chemistry Depositing user: Pure Administrator Date deposited: 23 Oct 2017 11:10 Last modified: 07 Aug 2024 01:29 Related URLs: URI: https://strathprints.strath.ac.uk/id/eprint/62120