A simple correlation of anodic peak potentials of silylarenes and their vertical ionization energies

The anodic oxidation potentials of a series of 16 silylarenes have been determined by cyclic voltammetry in acetonitrile. All oxidation steps have been found to be irreversible. The effect of substituents and substitution patterns on the oxidation potentials can be presented as a linear correlation between the experimental oxidation potentials and the calculated vertical ionization energies of the silylarenes, using correlated ab initio methods at the MP2 level of theory. This correlation is useful to predict oxidation and ionization potentials of other silylarenes.