Intramolecular electron transfer in bipyridinium disulfides

Gabriel B. Hall, Rudresha Kottani, Greg A N Felton, Takuhei Yamamoto, Dennis H. Evans, Richard S Glass, Dennis L Lichtenberger

Research output: Contribution to journalArticle

16 Citations (Scopus)

Abstract

Reductive cleavage of disulfide bonds is an important step in many biological and chemical processes. Whether cleavage occurs stepwise or concertedly with electron transfer is of interest. Also of interest is whether the disulfide bond is reduced directly by intermolecular electron transfer from an external reducing agent or mediated intramolecularly by internal electron transfer from another redox-active moiety elsewhere within the molecule. The electrochemical reductions of 4,4′-bipyridyl-3,3′-disulfide (1) and the di-N-methylated derivative (22+) have been studied in acetonitrile. Simulations of the cyclic voltammograms in combination with DFT (density functional theory) computations provide a consistent model of the reductive processes. Compound 1 undergoes reduction directly at the disulfide moiety with a substantially more negative potential for the first electron than for the second electron, resulting in an overall two-electron reduction and rapid cleavage of the S-S bond to form the dithiolate. In contrast, compound 22+ is reduced at less negative potential than 1 and at the dimethyl bipyridinium moiety rather than at the disulfide moiety. Most interesting, the second reduction of the bipyridinium moiety results in a fast and reversible intramolecular two-electron transfer to reduce the disulfide moiety and form the dithiolate. Thus, the redox-active bipyridinium moiety provides a low energy pathway for reductive cleavage of the S-S bond that avoids the highly negative potential for the first direct electron reduction. Following the intramolecular two-electron transfer and cleavage of the S-S bond the bipyridinium undergoes two additional reversible reductions at more negative potentials.

Original languageEnglish (US)
Pages (from-to)4012-4018
Number of pages7
JournalJournal of the American Chemical Society
Volume136
Issue number10
DOIs
StatePublished - Mar 12 2014

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Disulfides
Electrons
Oxidation-Reduction
Chemical Phenomena
Biological Phenomena
2,2'-Dipyridyl
Reducing Agents
Reducing agents
Acetonitrile
Density functional theory
Derivatives
Molecules

ASJC Scopus subject areas

  • Chemistry(all)
  • Catalysis
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Intramolecular electron transfer in bipyridinium disulfides. / Hall, Gabriel B.; Kottani, Rudresha; Felton, Greg A N; Yamamoto, Takuhei; Evans, Dennis H.; Glass, Richard S; Lichtenberger, Dennis L.

In: Journal of the American Chemical Society, Vol. 136, No. 10, 12.03.2014, p. 4012-4018.

Research output: Contribution to journalArticle

Hall GB, Kottani R, Felton GAN, Yamamoto T, Evans DH, Glass RS et al. Intramolecular electron transfer in bipyridinium disulfides. Journal of the American Chemical Society. 2014 Mar 12;136(10):4012-4018. https://doi.org/10.1021/ja500087m
Hall, Gabriel B. ; Kottani, Rudresha ; Felton, Greg A N ; Yamamoto, Takuhei ; Evans, Dennis H. ; Glass, Richard S ; Lichtenberger, Dennis L. / Intramolecular electron transfer in bipyridinium disulfides. In: Journal of the American Chemical Society. 2014 ; Vol. 136, No. 10. pp. 4012-4018.
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