Anodic oxidation of disulfides: Detection and reactions of disulfide radical cations

Kevin Lam, William E. Geiger

Research output: Contribution to journalArticlepeer-review

24 Citations (Scopus)

Abstract

The anodic oxidation of five diaryldisulfides have been studied in a dichloromethane/[NBu4][B(C6F5)4] electrolyte. Cyclic voltammetry scans of (p-RC6H4) 2S2 (R = Me, 1a; R = F, 1b; R = OMe, 1c) show modest chemical reversibility for the 10/+ couple (E1/2 values vs ferrocene: 1.04 V for 1a, 1.21 V for 1b, 0.92 V for 1c), providing the first voltammetric evidence for the radical cation [Ar2S2] +. A dimer dication, [Ar4S4]2+, is proposed as an intermediate in the formation of the electrolysis product, the trisulfide [Ar3S3]+. The chemical reversibility of the one-electron oxidations of Ar2S2 vanishes in [PF6]--containing electrolytes. The radical cations of the more sterically constrained ortho-substituted analogues dimesityldisulfide (2a, E1/2 = 1.01 V) and bis(2,4,6-triisopropylphenyl)disulfide (2b, E1/2 = 0.98 V) show less tendency to dimerize. In all cases except 2b, the bulk electrolysis product is [R3S3]+, consistent with earlier literature reports. A mechanism is proposed in which the trisulfide is formed by reaction of the dimer dication [Ar4S 4]2+ with neutral Ar2S2 to afford the trisulfide in a net 2/3 e- process. Oxidation of Ar 2S2, either anodically or by a strong one-electron oxidant, in the presence of cyclohexene gives an efficient synthetic route to 1,2-substituted cyclohexyldisulfides.

Original languageEnglish
Pages (from-to)8020-8027
Number of pages8
JournalJournal of Organic Chemistry
Volume78
Issue number16
DOIs
Publication statusPublished - Aug 16 2013

ASJC Scopus subject areas

  • Organic Chemistry

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