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Understanding Nickel (Pre-)Catalyst Activation, Speciation and Inhibition


   Department of Pure and Applied Chemistry

  ,  Monday, February 20, 2023  Funded PhD Project (UK Students Only)

About the Project

Nickel-catalysed methodology often relies on the in situ formation of an active catalyst from a nickel complex and an ancillary ligand. This can be ‘simple’ ligand exchange at a nickel(0) complex or the reduction of a nickel(II)/ligand complex to nickel(I) or nickel(0). When the ancillary ligand is an N-heterocyclic carbene (NHC), this is typically added as an azolium salt which must be deprotonated. The in situ formation of the active catalyst is convenient for screening reaction conditions or for high-throughput experimentation. However a lack of turnover might then be the result of the active catalyst: (i) being ineffective for the transformation of interest; (ii) forming too slowly or even not forming at all; (iii) being inhibited by pre-catalyst initiation by-products; or (iv) being unstable under the reaction conditions, and therefore prone to decomposition.

 This project will explore, in detail, the processes by which modern nickel(0) pre-catalysts generate active catalysts for a range of reactions of industrial importance. The project will also understand how the by-products of catalyst activation might affect the progress of the corresponding reactions.


Funding Notes

The project is supported by AstraZeneca and the Strathclyde Research Studentship Scheme (via a Research Excellence Award). This will include a three-month placement at AstraZeneca as part of a 36 or 42 month project. Funding will cover a stipend at no less than the UKRI rate, tuition fees (for home students only), costs for conference attendance, laboratory costs, and all costs associated with a placement at AstraZeneca.

References

For details of some of our previous work in the area, please see:
Inhibition of (dppf)nickel-catalysed Suzuki-Miyaura cross-coupling reactions by α-halo-N-heterocycles. A. K. Cooper, M. E. Greaves, W. Donohoe, P. M. Burton, T. O. Ronson, A. R. Kennedy, and D. J. Nelson, Chemical Science, 2021, 12, 14074
The Effect of Added Ligands on the Reactions of [Ni(COD)(dppf)] with Alkyl Halides: Halide Abstraction may be Reversible. M. E. Greaves, T. O. Ronson, F. Maseras, and D. J. Nelson, Organometallics, 2021, 40, 1997
Unexpected Nickel Complex Speciation Unlocks Alternative Pathways for the Reactions of Alkyl Halides with dppf-Nickel(0). M. E. Greaves, T. O. Ronson, G. C. Lloyd-Jones, F. Maseras, S. Sproules, and D. J. Nelson
ACS Catalysis, 2020, 10, 10717
Aldehydes and Ketones Influence Reactivity and Selectivity in Nickel-Catalyzed Suzuki-Miyaura Reactions. A. K. Cooper, D. K. Leonard, S. Bajo, P. M. Burton, and D. J. Nelson, Chemical Science, 2020, 11, 1905
Steric effects determine the mechanisms of reactions between bis(N-heterocyclic carbene)nickel(0) complexes and aryl halides. D. J. Nelson and F. Maseras, Chemical Communications, 2018, 54, 10646
Halide Abstraction Competes with Oxidative Addition in the Reactions of Aryl Halides with [Ni(PMenPh(3-n))4]. I. Funes-Ardoiz, D. J. Nelson, and F. Maseras, Chemistry - A European Journal, 2017, 23, 16728
Oxidative Addition of Aryl Electrophiles to a Prototypical Nickel(0) Complex: Mechanism and Structure/Activity Relationships. S. Bajo, G. Laidlaw, A. R. Kennedy, S. Sproules, and D. J. Nelson, Organometallics, 2017, 36, 1662

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