Stabilities of ion/radical adducts in the liquid phase as derived from the dependence of electrochemical cleavage reactivities upon solvent

The idea that significant ion/radical interactions should vary with solvent if they do exist in the liquid phase was pursued by an investigation of the dissociative electron-transfer reactivity of carbon tetrachloride and 4-cyanobenzyl chloride in four different solvents, 1,2-dichloroethane, NN-dimethylformamide, ethanol, and formamide, by means of their cyclic voltammetric responses. Modification of the conventional dissociative electron transfer theory to take account of an interaction between fragments in the ion/radical pair resulting from the dissociative electron reaction allows a satisfactory fitting of the experimental data leading to the determination of the interaction energy. There is an approximate correlation between the interaction energies in the ion/radical pair and the solvation free energies of the leaving anion, Cl-. The interaction is maximal in 1,2-dichloroethane, which is both the least polar and the least able to solvate Cl-. The interaction is smaller in the polar solvents, albeit distinctly measurable. The two protic solvents, ethanol and formamide, which are the most able to solvate Cl-, give rise to similar interaction energies. The interaction is definitely stronger in N,N-dimethylformamide, which has a lesser ability to solvate Cl- than the two other polar solvents. The existence of significant ion/radical interactions in polar media is thus confirmed and a route to their determination opened.