Distinction between stepwise and concerted mechanisms in reductive cleavage reactions—use of voltammetric current function in the analysis of non-linear kinetic laws

A systematic way of distinguishing stepwise and concerted mechanisms in reductive cleavage reactions has been formulated involving current function analysis of the voltammetric data. The electrochemical reductive cleavage of the carbon–iodine bond in 1,3-dichloro-2-iodobenzene has been analyzed from a mechanistic point of view to illustrate the methodology. 1,3-Dichloro-2-iodobenzene undergoes an initial stepwise electron transfer obeying quadratic activation-driving force relationship. The current function analysis yields the reorganization energy for the reduction of 1,3-dichloro-2-iodobenzene and the results have been verified independently using convolution potential sweep voltammetry.