Electrochemical reduction of 2, 4‐dimethyl(diethyl)‐9‐oxo‐10‐(4‐heptoxyphenyl)‐9H‐thioxanthenium hexafluorophosphates and 2, 4‐dimethyl(diethyl)‐9H‐thioxanthene‐9‐ones. (1st May 2018)

• Record Type: Journal Article
• Authors: Shundrin, Leonid A.; Avrorov, Pavel A.; Irtegova, Irina G.; Odintsov, Danila S.; Poveshchenko, Alexander F.
• Is Part Of: Journal of physical organic chemistry. Volume 31:Number 9(2018)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2018-05-01
• Subjects: cyclic voltammetry -- DFT calculations -- EPR spectroscopy -- radical anions -- thioxanthenium salts -- thioxanthenones; Chemistry, Physical organic -- Periodicals; 547.1
• DOI: 10.1002/poc.3853
• Languages: English
• ISSNs: 0894-3230

Abstract

Abstract: Electrochemical reduction of 2, 4‐dimethyl(diethyl)‐9‐oxo‐10‐(4‐heptoxyphenyl)‐ 9H ‐thioxanthenium hexafluorophosphates in acetonitrile (MeCN) and N, N ‐dimethylformamide 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. Abstract : Electrochemical reduction of 2, 4‐dimethyl(diethyl)‐9‐oxo‐10‐(4‐heptoxyphenyl)‐9 H ‐thioxanthenium hexafluorophosphates in acetonitrile (MeCN) and N, N‐dimethylformamide is an irreversible one‐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. The latter compounds are reduced reversibly at more negative potentials and yields the corresponding radical anions which have been characterized by EPR spectroscopy and DFT calculations at the (U)B3LYP/6‐31+G*/PCM level of theory.