Application of the dissociative electron transfer theory and its extension to the case of in-cage interactions in the electrochemical reduction of arene sulfonyl chlorides.

Important aspects of the electrochemical reduction of a series of substituted arene sulfonyl chlorides are investigated. An interesting autocatalytic mechanism is encountered where the starting material is reduced both at the electrode and through homogeneous electron transfer from the resulting sulfinate anion. This is due to the homogenous electron transfer from the two-electron reduction produced anion (arene sulfinate) to the parent arene sulfonyl chloride. As a result, the reduction process and hence the generated final products depend on both the concentration of the substrate and the scan rate. A change is also observed in the reductive cleavage mechanism as a function of the substituent on the phenyl ring of the arene sulfonyl chloride. With 4-cyano and 4-nitrophenyl sulfonyl chlorides a "sticky" dissociative ET mechanism takes place where a concerted ET mechanism leads to the formation of a radical/anion cluster before decomposition. With other substituents (MeO, Me, H, Cl, and F) a "classical" dissociative ET is followed, where the ET and bond cleavage are simultaneous. The dissociative electron transfer theory, as well as its extension to the case of strong in-cage interactions between the produced fragments, along with gas phase chemical quantum calculations results helped us to rationalize both the observed change in the ET mechanism and the occurrence of the "sticky" dissociative ET mechanism. The radical/anion pair interactions have been determined both in solution as well as in the gas phase. The study also shows that despite the low magnitude of in-cage interactions in acetonitrile compared to the gas phase their existence strongly affects the dynamics of the involved reactions. It also shows that, as expected, these interactions are reinforced by the existence of strong electron-withdrawing substituents. The occurrence of an autocatalytic process and the existence of the radical/anion interaction may explain the differences previously observed in the reduction of these compounds in different media.