Theoretical investigation of aniline derivatives: Correlation of theoretical reaction Gibbs free energies with experimental oxidation potentials

Anilines and their derivatives are used in industrial production of dyes, pharmaceuticals, plastics, and synthetic antioxidants. Abstraction of electron and formation of a cation radical represent a significant step in the reactivity of this group of substances. The aim of this study was to theoretically investigate the effect of a substituent on the oxidative electrochemical potential of 64 species of aniline derivatives. Quantum-chemical calculations were performed using the composite G4 method. The obtained linear dependences for reaction Gibbs free energies were correlated with the Hammett constants and available experimental values.