Electrochemical reduction of 2,4‐dimethyl(diethyl)‐9‐oxo‐10‐(4‐heptoxyphenyl)‐9H‐thioxanthenium hexafluorophosphates and 2,4‐dimethyl(diethyl)‐9H‐thioxanthene‐9‐ones |
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| Authors: | Leonid A Shundrin Pavel A Avrorov Irina G Irtegova Danila S Odintsov Alexander F Poveshchenko |
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| Institution: | 1. N. N. Vorozhtsov Institute of Organic Chemistry, Russian Academy of Sciences, Novosibirsk, Russia;2. Department of Natural Sciences, Novosibirsk State University, Novosibirsk, Russia;3. The Scientific Institute of Clinical and Experimental Lymphology, Russian Academy of Medical Sciences, Novosibirsk, Russia |
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| 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. |
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| Keywords: | cyclic voltammetry DFT calculations EPR spectroscopy radical anions thioxanthenium salts thioxanthenones |
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