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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, Murphy, Damien M. 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: 23 Jul 2019 09:05
URI: http://orca.cf.ac.uk/id/eprint/120494

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