Electrochemical reduction of organic and organometallic compounds. Polarization effect in radical anions

Half-wave potentials of electrochemical reduction and electron affinities of X-B-RC compounds belonging to 23 reaction series depend not only on the inductive and resonance effects but also on the polarization effect of the X substituent, which was not taken into account previously. In some cases, the contribution of the polarization effect reaches 50% of the overall substituent effect. The main factors responsible for the magnitude of polarization effect in X-B-RC∸ radical anions are the natures of reaction center RC and bridging moiety B and the distance between the substituent X and reaction center RC.