ELECTRON TRANSFER FROM AROMATIC HYDROCARBONS AND THEIR pi -COMPLEXES WITH METALS. COMPARISON OF THE STANDARD OXIDATION POTENTIALS AND VERTICAL IONIZATION POTENTIALS.

Article abstract of DOI:10.1021/ja00326a014

The energetics of electron transfer from an extensive series of alkyl-substituted benzenes are measured both in solution and in the gas phase. The standard oxidation potentials E//A//r degree stem from the reversible cyclic voltammograms (CV) in trifluoroacetic acid using the recently developed microvoltammetric electrodes. These values show an excellent correlation with the vertical ionization potentials I//p of the same aromatic hydrocarbons in the gas phase. Thermochemical analysis indicates that the slope of less than unity for the correlation arises mainly from solvation differences, particularly in the highly substituted polyalkylbenzenes.