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

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

doi:10.1002/chem.201702331

Halide abstraction competes with oxidative addition in the reactions of aryl halides with [Ni(PMe_nPh(_3-n))₄]

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

Pure And Applied Chemistry

Research output: Contribution to journal › Article

14 Citations (Scopus)

Abstract

Density functional theory (DFT) calculations have been used to study the oxidative addition of aryl halides to complexes of the type [Ni(PMe_nPh_(3-n))₄], revealing the crucial role of an open shell singlet transition state for halide abstraction. The formation of NiI versus Ni^II has been rationalised through the study of three different pathways: (i) halide abstraction by [Ni(PMe_nPh_(3-n))₃], via an open shell singlet transition state; (ii) S_N2-type oxidative addition to [Ni(PMe_nPh_(3-n))₃], followed by phosphine dissociation; and (iii) oxidative addition to [Ni(PMe_nPh_(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 Ni^II. Importantly, [Ni(PMe_nPh_(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.

Language	English
Pages	16728-16733
Number of pages	6
Journal	Chemistry - A European Journal
Volume	23
Issue number	66
Early online date	20 Nov 2017
DOIs	10.1002/chem.201702331
Publication status	Published - 27 Nov 2017

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phosphine

Addition reactions

Catalysis

Density functional theory

Ligands

Keywords

density fuctional calculations
homogenous catalysis
nickel
electron transfer
ligand effects

Cite this

Funes-Ardoiz, I., Nelson, D. J., & Maseras, F. (2017). Halide abstraction competes with oxidative addition in the reactions of aryl halides with [Ni(PMe_nPh(_3-n))₄]. Chemistry - A European Journal, 23(66), 16728-16733. https://doi.org/10.1002/chem.201702331

Funes-Ardoiz, Ignacio ; Nelson, David J. ; Maseras, Feliu. / Halide abstraction competes with oxidative addition in the reactions of aryl halides with [Ni(PMe_nPh(_3-n))₄]. In: Chemistry - A European Journal. 2017 ; Vol. 23, No. 66. pp. 16728-16733.

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

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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Funes-Ardoiz, I, Nelson, DJ & Maseras, F 2017, 'Halide abstraction competes with oxidative addition in the reactions of aryl halides with [Ni(PMe_nPh(_3-n))₄]' Chemistry - A European Journal, vol. 23, no. 66, pp. 16728-16733. https://doi.org/10.1002/chem.201702331

Halide abstraction competes with oxidative addition in the reactions of aryl halides with [Ni(PMe_nPh(_3-n))₄]. / Funes-Ardoiz, Ignacio; Nelson, David J.; Maseras, Feliu.

In: Chemistry - A European Journal, Vol. 23, No. 66, 27.11.2017, p. 16728-16733.

Research output: Contribution to journal › Article

TY - JOUR

T1 - Halide abstraction competes with oxidative addition in the reactions of aryl halides with [Ni(PMenPh(3-n))4]

AU - Funes-Ardoiz, Ignacio

AU - Nelson, David J.

AU - Maseras, Feliu

PY - 2017/11/27

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N2 - 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.

AB - 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.

KW - density fuctional calculations

KW - homogenous catalysis

KW - nickel

KW - electron transfer

KW - ligand effects

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