Unexpected nickel complex speciation unlocks alternative pathways for the reactions of alkyl halides with dppf-nickel(0)

Greaves, M. , Ronson, T. O. , Lloyd-Jones, G. C. , Maseras, F. , Sproules, S. and Nelson, D. J. (2020) Unexpected nickel complex speciation unlocks alternative pathways for the reactions of alkyl halides with dppf-nickel(0). ACS Catalysis, 10(18), pp. 10717-10725. (doi: 10.1021/acscatal.0c02514)

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Abstract

The mechanism of the reactions between dppf-Ni0 complexes and alkyl halides has been investigated using kinetic and mechanistic experiments and DFT calculations. The active species is [Ni(κ2-dppf)(κ1-dppf)], which undergoes a halide abstraction reaction with alkyl halides and rapidly captures the alkyl radical that is formed. The rates of the reactions of [Ni(COD)(dppf)] with alkyl halides and the yields of prototypical nickel-catalysed Kumada cross-coupling reactions of alkyl halides are shown to be significantly improved by the addition of free dppf ligand.

Item Type:Articles
Status:Published
Refereed:Yes
Glasgow Author(s) Enlighten ID:Sproules, Dr Stephen
Authors: Greaves, M., Ronson, T. O., Lloyd-Jones, G. C., Maseras, F., Sproules, S., and Nelson, D. J.
College/School:College of Science and Engineering > School of Chemistry
Journal Name:ACS Catalysis
Publisher:American Chemical Society
ISSN:2155-5435
ISSN (Online):2155-5435
Published Online:21 August 2020
Copyright Holders:Copyright © American Chemical Society
First Published:First published in ACS Catalysis 10(18):10717–10725
Publisher Policy:Reproduced under a Creative Commons License

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