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

Research output: Contribution to journalArticle

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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.
Original languageEnglish
Pages (from-to)16728-16733
Number of pages6
JournalChemistry - A European Journal
Volume23
Issue number66
Early online date20 Nov 2017
DOIs
Publication statusPublished - 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

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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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Halide abstraction competes with oxidative addition in the reactions of aryl halides with [Ni(PMenPh(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 journalArticle

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

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KW - electron transfer

KW - ligand effects

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