Studies of the EE mechanism. Evidence for reversible dimer formation in electrochemical oxidation of a cyclic dithioether

M. D. Ryan, D. D. Swanson, R. S. Glass, G. S. Wilson

Research output: Contribution to journalArticle

47 Scopus citations

Abstract

The electrochemical oxidation of 1,5-dithiacyclooctane (DTCO) in acetonitrile has been shown to result in two closely spaced (ΔE ≈ 20 mV) reversible one-electron-transfer steps. A reversible second-order chemical reaction is observed to follow production of the cation radical thus resulting in dimer formation. As the dimer is not electroactive at the potential of the initial process, its further oxidation or reduction must be preceded by dissociation. These conclusions are supported by cyclic voltammetry, controlled potential electrolysis, rotating disk electrode studies, and semiintegral analysis. The unusual ease of the second electron-transfer step is attributed to interactions between the two mesocyclic sulfur atoms.

Original languageEnglish (US)
Pages (from-to)1069-1075
Number of pages7
JournalJournal of physical chemistry
Volume85
Issue number8
DOIs
StatePublished - Jan 1 1981

ASJC Scopus subject areas

  • Engineering(all)
  • Physical and Theoretical Chemistry

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