Article
Synthesis, Electrochemistry, and Gas-Phase Photoelectron Spectroscopic and Theoretical Studies of 3,6-Bis(perfluoroalkyl)-1,2-dithiins
The University of Arizona.
In papers with more than one author, the asterisk indicates the name of the author to whom inquiries about the paper should be addressed.
State University of New York at Albany.
Abstract

3,6-Bis(trifluoromethyl)- and 3,6-bis(pentafluoroethyl)-1,2-dithiin (1a,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 1a and 1b 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 1a and 1b 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.
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History
- Published In Issue October 17, 2003
- Received May 21, 2003
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