Reductive cleavage of dichalcogenide bonds 3. Selectivity of electron exchange in diaryldichalcogenide-bispyridinium systems

The kinetics of reductive cleavage of the dichalcogenide bond in dimeric Sc hiff's bases ArEEAr (E = S, Te) induced by indirect electron transfer by in situ generated bridged bispyridinium radical cations and biradicals was st udied by cyclic voltammetry. It was shown that the dependence between the a pparent rate constants of intermolecular electron transfer and the electron -withdrawing properties of diaryldichalcogenides is violated. The mechanism s of homogeneous (chemical) and heterogeneous (electrochemical) reductive c leavage of diaryldichalcogenides were discussed.