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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.
Original languageEnglish
Pages (from-to)1706-1713
Number of pages8
JournalElectroanalysis
Volume30
Issue number8
Early online date6 Apr 2018
DOIs
Publication statusPublished - 1 Aug 2018

Keywords

  • C−H abstraction
  • TEMPO
  • fuel.
  • radicalisation
  • redox mediator
  • voltammetry

ASJC Scopus subject areas

  • Analytical Chemistry
  • Electrochemistry

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