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)

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