2,2,6,6-Tetramethyl piperidine-1-oxyl (TEMPO)-mediated catalytic oxidation of benzyl alcohol in acetonitrile and ionic liquid 1-butyl-3-methyl-imidazolium hexafluorophosphate [BMIm][PF6]: Kinetic analysis

Ajith C. Herath, James Y. Becker

Research output: Contribution to journalArticlepeer-review

45 Scopus citations

Abstract

TEMPO (2,2,6,6-tetramethyl piperidine-1-oxyl) is electrochemically oxidized to a stable form of the cation (TEMPO+) in acetonitrile (CH3CN) or 1-butyl-3-methyl-imidazolium hexafluorophosphate ([BMIm][PF6]) media. Cyclic voltammograms were characterized by a well-defined one-electron reversible redox couple in both media at low scan rates. The reduced form of TEMPO+ is catalytically regenerated in a follow-up chemical reaction with benzyl alcohol (BA) in the presence of 2,6-lutidine. It was observed that in [BMIm][PF6], the redox currents are largely suppressed compared to that in CH3CN. The apparent heterogeneous electron-transfer rate constant (kapp0) of the quasi-reversible redox reaction of TEMPO was determined at a Pt electrode and found to be 1.9 × 10-3 cm s-1 and 4.5 × 10-2 cm s-1 in [BMIm][PF6] and CH3CN, respectively. With the aid of chronoamperometry (CA), the homogeneous rate constant for the catalytic oxidation of benzyl alcohol by TEMPO, in the presence of 2,6-lutidine in CH3CN was estimated to be 5.53 × 101 M-1 s-1 which is approximately double, relative to the value of 2.91 × 101 M-1 s-1 determined in [BMIm][PF6].

Original languageEnglish
Pages (from-to)4324-4330
Number of pages7
JournalElectrochimica Acta
Volume53
Issue number12
DOIs
StatePublished - 1 May 2008

Keywords

  • Benzyl alcohol
  • Catalytic current
  • Ionic liquid
  • Rate constant
  • TEMPO

ASJC Scopus subject areas

  • Chemical Engineering (all)
  • Electrochemistry

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