Electron reduction processes of nitrothiophenes. A systematic approach by DFT computations, cyclic voltammetry and E-ESR spectroscopy

Abstract

In the framework of the interest in nitrothiophenes as drugs or hits with different pharmacological applications and considering that in several instances nitroreduction is an essential step for their biological activity, we have studied a complete series of mono-, di-, and tri-nitrothiophenes (1–6) and by comparison some mononitro benzo[b]thiophenes and benzo[b]furans (7–10). Their electroreduction behaviour has been investigated by different techniques: DFT calculations, cyclic voltammetry and electrochemical electron spin resonance spectroscopy. Although, the first reduction process for all of the compounds leads to the relevant radical anions, both the computational and experimental results indicate that there are significant differences in the fate of their corresponding forthcoming reductions, for example, formation of secondary radicals (open-shell electronic structures) or dianions. The effect of the relative positions of the nitro groups during the reduction has also been analysed and rationalised.