RADICAL CATION INTERMEDIATES IN THE FORMATION OF SCHIFF BASES ON IRRADIATED SEMICONDUCTOR POWDERS

Article abstract of DOI:10.1016/S0040-4020(01)88091-1

Photocatalytic oxidation of several primary aliphatic amines on irradiated TiO2 powders suspended in anhydrous acetonitrile led to good yields of the corresponding symmetrical N-alkylidene amines.Mechanistic electrochemical investigation of the reaction revealed intermediate formation of an immonium cation in an ECE route.This species is generated via electrooxidation of an α-amino radical formed by deprotonation of the primary oxidation product, an aminium cation radical.The influence of the metal oxide surface on radical cation reactivity is discussed.