Electrochemically driven C-H hydrogen abstraction processes with the tetrachloro-phthalimido-N-oxyl (Cl4PINO) catalyst

Buckingham, Mark A., Cunningham, William, Bull, Steven D., Buchard, Antoine, Folli, Andrea ORCID: https://orcid.org/0000-0001-8913-6606, Murphy, Damien M. ORCID: https://orcid.org/0000-0002-5941-4879 and Marken, Frank 2018. Electrochemically driven C-H hydrogen abstraction processes with the tetrachloro-phthalimido-N-oxyl (Cl4PINO) catalyst. Electroanalysis 30 (8) , pp. 1698-1705. 10.1002/elan.201800147

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Abstract

The radical redox mediator tetrachloro-phthalimido-N-oxyl (Cl4PINO) is generated at a glassy carbon electrode and investigated for the model oxidation of primary and secondary alcohols with particular attention to reaction rates and mechanism. The two-electron oxidation reactions of a range of primary, secondary, and cyclic alcohols are dissected into an initial step based on C-H hydrogen abstraction (rate constant k1, confirmed by kinetic isotope effect) and a fast radical-radical coupling of the resulting alcohol radical with Cl4PINO to give a ketal that only slowly releases the aldehyde/ketone and redox mediator precursor back into solution (rate constant k2). In situ electrochemical EPR reveals Cl4PINO sensitivity towards moisture. DFT methods are applied to confirm and predict C-H hydrogen abstraction reactivity.

Item Type:	Article
Date Type:	Publication
Status:	Published
Schools:	Chemistry
Publisher:	Wiley
ISSN:	1040-0397
Date of First Compliant Deposit:	11 April 2019
Date of Acceptance:	17 March 2018
Last Modified:	27 Nov 2024 00:30
URI:	https://orca.cardiff.ac.uk/id/eprint/120494

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