Collect. Czech. Chem. Commun. 1997, 62, 855-865

Radical Intermediates in Photochemical and Redox Initiated Decomposition of Thioazo Compounds(an EPR and Cyclovoltammetric Study)

Katarína Erentováa, Vladimír Adamčíka, Andrej Staškoa, Oskar Nuykenb, Arming Langb and Michael B. Leitnerc

a Department of Physical Chemistry, Slovak Technical University, 812 37 Bratislava, Slovak Republic
b Department of Makromolecular Chemistry, Technical University Munich, Lichtenbergerstrasse 4, 857 47 Garching, Germany
c Department of Technical Chemistry, Technical University Berlin, Strasse des 17. Juni 135,10623 Berlin, Germany


The cathodically and photochemically induced decomposition of thioazo compounds XC6H4-N2-S-C6H4CH3 and their polymers with X = NO2, COOH, and SO3H were investigated. The formation of carbon-centered XC6H4. and sulfur-centered .S-C6H4Y radicals was confirmed using spin-trap technique. These reactive radicals either abstract hydrogen from CH3CN solvent molecule forming .CH2CN radical or they recombine to cage products XC6H4-S-C6H4CH3 eliminating N2. The decomposition rate of the investigated thioazo compounds is characterized by a formal half-life time of 5 to 10 s.

Keywords: Photolysis; Free radicals; Electrochemically initiated decomposition; Spin trap.