Electrochemical reduction of 2,4‐dimethyl(diethyl)‐9‐oxo‐10‐(4‐heptoxyphenyl)‐9H‐thioxanthenium hexafluorophosphates and 2,4‐dimethyl(diethyl)‐9H‐thioxanthene‐9‐ones

Abstract

Electrochemical reduction of 2,4-dimethyl(diethyl)-9-oxo-10-(4-heptoxyphenyl)-9H-thioxanthenium hexafluorophosphates in acetonitrile (MeCN) and N,Ndimethylformamide is an irreversible 1-electron process accompanied by the cleavage of the C(Ph)-S bond in thioxanthenium cations with the formation of the corresponding 2,4-dimethyl(diethyl)-9H-thioxanthene-9-ones. One-electron reversible electrochemical reduction of the latter compounds occurs at more negative potentials and yields the corresponding radical anions, which have been characterized by electron paramagnetic resonance spectroscopy and density functional theory calculations at the (U)B3LYP/6-31+G*/polarizable continuum model level of theory.