Electrochemical and chemical oxidation of dithia-, diselena-, ditellura-, selenathia-, and tellurathiamesocycles and stability of the oxidized species

Dennis H. Evans, Nadine E. Gruhn, Jin Jin, Bo Li, Edward Lorance, Noriko Okumura, Norma A. Macías-Ruvalcaba, Uzma I. Zakai, Shao Zhong Zhang, Eric Block, Richard S. Glass

Research output: Contribution to journalArticlepeer-review

19 Scopus citations

Abstract

"Chemical Equation Presented" The diverse electrochemical and chemical oxidations of dichalcogena-mesocycles are analyzed, broadening our understanding of the chemistry of the corresponding radical cations and dications. 1,5-Diselenocane and 1,5-dithiocane undergo reversible two-electron oxidation with inverted potentials analogous to 1,5-dithiocane. On the other hand, 1,5-selenathiocane and 1,5-tellurathiocane undergo one-electron oxidative dimerization. The X-ray crystal structures of the Se-Se dimer of the 1,5-selenathiocane one-electron oxidized product and the monomeric two-electron oxidized product (dication) of 1,5-tellurathiocane are reported. 1,5-Dithiocanes and 1,5-diselenocanes with group 14 atoms as ring members undergo irreversible oxidation, unlike the reversible two-electron oxidation of the corresponding silicon-containing 1,5-ditellurocanes. These results demonstrate the chemical consequences of the dication stabilities Te+-Te+ > Se+-Se+> S+-S+, as well as Se+-Se+ > Se+-S+ and Te +-Te+ > Te+-S+.

Original languageEnglish (US)
Pages (from-to)1997-2009
Number of pages13
JournalJournal of Organic Chemistry
Volume75
Issue number6
DOIs
StatePublished - Mar 19 2010

ASJC Scopus subject areas

  • Organic Chemistry

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