The effect of substituents on the anodic oxidation of aliphatic carboxylates and the passage towards a pseudo-Kolbe reaction

► The pseudo-Kolbe reaction as an example of intramolecular dissociative electron transfer. ► Correlation between the vertical ionization potential with oxidation peak potentials. ► The effect of substituents on the mechanism of anodic oxidation of aliphatic carboxylates. ► The mechanism of the anodic oxidation of tetrabutylammonium carboxylates in acetonitrile.