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Australian Journal of Chemistry Australian Journal of Chemistry Society
An international journal for chemical science
RESEARCH ARTICLE

On the Electrochemical-Behavior of Pyrylium Ions at the Mercury-Electrode. II. Aromatically Substituted Ions in Acetonitrile

WNC Garrard and FG Thomas

Australian Journal of Chemistry 39(6) 865 - 884
Published: 1986

Abstract

The electrochemical behaviour of the 2,4,6-triphenylpyrylium ( tpp +) and 7-phenyl-5,6,8,9-tetrahydrodibenzo[ c,h ] xanthylium (thx+) ions in acetonitrile in the presence of 0.1 M tetrabutylammonium perchlorate is reported. The reduction of both ions proceeds by two, one-electron steps. The initial product of the first reduction is the corresponding radical, which may dimerize to give isomeric bipyrans in the case of tpp + or a phenyl-phenyl or phenyl- pyranyl dimer in the case of thx+. The corresponding anions are the initial products of the second reduction step. The tpp - anion reacts with tpp + to give the bipyran while the thx- anions appear to undergo polymerization reactions with thx+. Both tpp + and thx+ and their reduction products are adsorbed at the mercury electrode. In the adsorbed state thx+ forms one of two surface phases depending on the potential, one with the molecules in a flat orientation and the other, a condensed phase, with vertically oriented molecules. Perchlorate ions are considered to be co-adsorbed with the cations.

https://doi.org/10.1071/CH9860865

© CSIRO 1986

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