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. © 2004 Elsevier Ltd. All rights reserved.