Abstract
The mechanistic and kinetic details of the ECE-type anodic oxidation in acetonitrile of eight methyl benzenes are investigated using electrochemical and spectroelectrochemical methods. It is shown how the latter techniques enable a clear distinction to be made for the first time between ECE and disproportionation (DISP) mechanisms. Detailed fitting of the spectroelectrochemical data for the three intermediates (cation radical, neutral radical and carbonium ion) from two of the substrates enabled most of the chemical rate constants involved in the DISP 1 mechanism to be evaluated. Values for λ max for the major uv-visible absorbances together with extinction coefficients are given for most of the intermediates.
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