Numerical Modeling of ECE‐ECE and Parallel EE‐EE Mechanisms in Cyclic Voltammetry. Reduction of 1,4‐Benzenedisulfonyl Difluoride and 1,4‐Naphthalenedisulfonyl Difluoride

A numerical model of the process where the ECE‐ECE sequence competes with the parallel EE‐EE mechanisms of reduction has been developed. The ECE‐ECE / EE‐EE model was applied to complex, experimentally observed processes, in which the parallel path of anion‐radical reduction could be expected. The applicability of the proposed model was examined experimentally for two chemical systems: (i) 1,4‐benzenedisulfonyl difluoride (1,4‐BDF) and (ii) 1,4‐naphthalenedisulfonyl difluoride (1,4‐NDF). For both model compounds the reduction processes on Hg and glassy carbon electrodes were investigated by means of cyclic voltammetry performed in DMF solutions containing 0.3 M of TBAP. In contrast to other reductive cleavage reactions such as the fragmentation of the C‐Hal–type bond, the electro‐reduction of anion‐radicals ArSO₂F^?. was evident. The elementary kinetic parameters of the process are determined and discussed.