The cathodic behaviour of poly(alkyl) and (aryl) sulfones revisited. Mechanistic and theoretical approaches

A series of aromatic sulfones activated by 2, 3 or 4 sulfonyl groups were reduced electrochemically in aprotic media. The electrochemical behaviour is strongly directed by the nature and the number of the substituents bound to the aromatic ring. From the analyses of cyclic voltammetry experiments, the kinetics and thermodynamic parameters were evaluated for each system and a theoretical study at the B3LYP/6-31G* level was performed simultaneously to understand the reactivity of the radical anions stemmed from these aromatic sulfones.