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The electrochemical behavior of thianthrenes 1-4, of selenanthrenes 5-8 (dibenzo-1,4-dichal- cogenins). of 2,2′-dithiobiphenyls 9 and 10 (dibenzo-1,2-dichalcogenins) as well as of the related compounds 11-13 were studied by cyclic voltammetry in acetonitrile. All dibenzodichalcogenins can be [oxidised in two one-electron-steps, the processes being totally reversible for 7, nearly reversible for 2 and 9, quasireversible for 1, 3, 4,10 and 13, and irreversible in all other cases. For 1- 4, 7, 9, 10 and 13 the diffusion coefficients of the electrochemically active species and the rate constants of the electron transfer are calculated from the potentials measured. Electrolysis of 9 in dichloromethane with tetrabutylammonium perchlorate as supporting elec­trolyte yields [dithiobiphenyl]  +  [C10 4 ] -  (14), while oxidation by nitrosyl hexachloroantimonate gives [(dithiobiphenyl) 2 ]  +  [SbCl 6 ] -  (15).

zeitschrift für naturforschung b

Elektrochemisches Verhalten von Dibenzodichalkogeninen und verwandten Verbindungen / Electrochemical Behavior of Dibenzodichalcogenins and Related Compounds