A mechanistic study on the anodic oxidation of 1,1-dimethylallene (DMA). A semi-empirical method for resolving irreversible overlapping waves in cyclic voltammetry

The anodic oxidation of the titled compound has been studied in acetonitrile at a platinum anode in the presence of tetraethylammoniumfluoborate and lithium perchlorate as supporting electrolytes. In the presence of the former electrolyte the cylcic voltammogram exhibits two moderately separated waves, whereas in the presence of the latter the waves overlap each other completely. An ECE mechanism is proposed in either electrolyte. The two moderately overlapping waves obtained for the oxidation of DMA in the presence of BF₄^- have been resolved into two separate waves with equal heights, by employing a semi-empirical method. Studies of the effect of electrolyte concentration on the shift in anodic peak potentials are presented and discussed in terms of specific and non-specific adsorption of ClO₄^- and BF₄^-.