Projects per year
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 language | English |
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Pages (from-to) | 16728-16733 |
Number of pages | 6 |
Journal | Chemistry - A European Journal |
Volume | 23 |
Issue number | 66 |
Early online date | 20 Nov 2017 |
DOIs | |
Publication status | Published - 27 Nov 2017 |
Keywords
- density fuctional calculations
- homogenous catalysis
- nickel
- electron transfer
- ligand effects
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Projects
- 2 Finished
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Global Engagements- Institut Catalá d’Investigació Química (ICIQ)
Nelson, D. & Maseras, F.
2/02/15 → 1/02/16
Project: Internally funded project
Datasets
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Data for: "Halide abstraction competes with oxidative addition in the reactions of aryl halides with [Ni(PMenPh(3-n))4]"
Funes-Ardoiz, I. (Creator), Nelson, D. (Creator) & Maseras, F. (Creator), 3 Jul 2019
DOI: 10.19061/iochem-bd-1-55, https://doi.org/10.1002/chem.201702331
Dataset
Research output
- 36 Citations
- 1 Letter
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Steric effects determine the mechanisms of reactions between bis(N-heterocyclic carbene)-nickel(0) complexes and aryl halides
Nelson, D. J. & Maseras, F., 29 Aug 2018, (Accepted/In press) In: Chemical Communications. p. 1-3 3 p.Research output: Contribution to journal › Letter › peer-review
Open AccessFile
Activities
- 3 Invited talk
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Understanding Oxidative Addition to Nickel(0): Implications for Cross-Coupling Catalysis
David Nelson (Speaker)
11 Oct 2019Activity: Talk or presentation types › Invited talk
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Nickel(0) Complexes and Aryl Halides: Reaction Mechanisms and Structure/Reactivity Relationships
David Nelson (Keynote speaker)
10 Jul 2018Activity: Talk or presentation types › Invited talk
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Dialing Molecules with Nickel Catalysis: Understanding Oxidative Addition to Nickel(0) Complexes Relevant to Cross-Coupling
David Nelson (Speaker)
4 Jan 2018Activity: Talk or presentation types › Invited talk