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.
LanguageEnglish
Pages1706-1713
JournalElectroanalysis
Volume30
Issue number8
Early online date6 Apr 2018
DOIs
StatusPublished - 1 Aug 2018

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Hydrogen
Alcohols
Catalysts
Rate constants
Oxidation
Glassy carbon
Ketones
Aldehydes
Discrete Fourier transforms
Isotopes
Reaction rates
Paramagnetic resonance
Moisture
Electrodes
Kinetics
Electrons
Oxidation-Reduction

Cite this

Electrochemically Driven C-H Hydrogen Abstraction Processes with the Tetrachloro-Phthalimido-N-Oxyl (Cl4PINO) Catalyst. / Marken, Frank; Buckingham, Mark A.; Bull, Steven; Cunningham, William; Buchard, Antoine; Folli, Andrea; Murphy, Damien.

In: Electroanalysis, Vol. 30, No. 8, 01.08.2018, p. 1706-1713.

Research output: Contribution to journalArticle

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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.",
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AU - Bull, Steven

AU - Cunningham, William

AU - Buchard, Antoine

AU - Folli, Andrea

AU - Murphy, Damien

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N2 - 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.

AB - 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.

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