The Effect of Proton Donors on the Process of Electrochemical Generation of Thiocyanogen and Its Reactivity

In continuation of our systematic study of the mechanism of thiocyanogen generation via electrochemical oxidation of thiocyanate anion in acetonitrile, the influence of proton donors both on the generation and on the reactivity of thiocyanogen itself was studied by experimental (cyclic voltammetry, electrolysis) and theoretical (digital simulations, quantum chemical calculations) methods. In a series of acids of various strengths (acetic, trifluoroacetic and perchloric acids), the effect was revealed only in the case of a strong proton donor, perchloric acid. It was shown that perchloric acid forms with thiocyanogen a hydrogen-bonded complex, less active in the thiocyanation reaction.