Electrochemical oxidations of 4-methylcatechol (1), 4-tert-butylcatechol (5) and catechol (7) in the presence of different nucleophiles have been investigated both experimentally and theoretically. Experimental results have been obtained by means of cyclic voltammetry and controlledpotential coulometry. Also the theoretical results were calculated at DFT (B3LYP) level of theory and 6–311+G (p, d) basis set. The calculated results indicate that oxidation potential of catechols (1, 5, 7) and their substituted species are directly dependent on the ΔGtot, and continuance of reactions during electrolysis is dependent on ΔGtot of produced species on the surface of electrode. The current study indicates that theoretical studies along with empirical research can be useful in displaying electrochemical reaction mechanisms.
