Synthesis, electrochemistry, and gas-phase photoelectron spectroscopic and theoretical studies of 3,6-bis(perfluoroalkyl)-1,2-dithiins

Edward D. Lorance, Richard S. Glass, Eric Block, Xiaojie Li

Research output: Contribution to journalArticlepeer-review

20 Scopus citations


3,6-Bis(trifluoromethyl)- and 3,6-bis(pentafluoroethyl)-1,2-dithiin (la,b), the first known perfluoroalkyl-substituted 1,2-dithiins, were synthesized from (Z,Z)-1,4-bis(tert-butylthio)-1,3-butadiene (2) to evaluate the effects of electron-withdrawing groups on the ionization and oxidation potentials of 1,2-dithiins. Analysis of the photoelectron spectra of la and lb provided a basis for assigning orbital compositions. Ab initio calculations on these compounds showed that they adopt a twist geometry as does 1,2-dithiin (1c) itself. Cyclic voltammetric studies on la and lb revealed a reversible oxidation followed by an irreversible oxidation at much more positive potentials than for 1,2-dithiin and 3,6-dimethyl-1,2-dithiin (1d). The oxidation potentials determined electrochemically do not correlate with the ionization potentials determined by photoelectron spectroscopy. This result supports the previously advanced hypothesis that there is a geometry change on electrochemical oxidation leading to a planar radical cation.

Original languageEnglish (US)
Pages (from-to)8110-8114
Number of pages5
JournalJournal of Organic Chemistry
Issue number21
StatePublished - Oct 17 2003

ASJC Scopus subject areas

  • Organic Chemistry


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