Radical anions containing the dioxidated 1,2,5‐thiadiazole heterocycle |
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| Authors: | María Virginia Mirífico José Alberto Caram Ana María Gennaro Carlos Jorge Cobos Enrique Julio Vasini |
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| Affiliation: | 1. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas Aplicadas (INIFTA, CCT La Plata‐CONICET), Facultad de Ciencias Exactas, Departamento de Química, Universidad Nacional de La Plata, Casilla de Correo 16, Sucursal 4, (1900) La Plata, Argentina;2. Facultad de Ingeniería, área Departamental Ingeniería Química, Universidad Nacional de La Plata, Calle 47 y 1, (1900) La Plata, Argentina;3. Instituto de Desarrollo Tecnológico para la Industria Química, INTEC. Güemes 3450, 3000 Santa Fe, and Facultad de Bioquímica y Ciencias Biológicas, UNL Santa Fe, Argentina |
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| Abstract: | Radical anions of 3,4‐aryl disubstituted 1,2,5‐thiadiazole 1,1‐dioxide were obtained by chemical and electrochemical reduction of their substrates, and characterized by ESR spectroscopy and cyclic voltammetry. The radical anion of the phenanthro[9,10‐c]‐1,2,5‐thiadiazole 1,1‐dioxide was found to be very stable in an aprotic solvent solution and did not react readily when water was added to the aprotic solvent, or the solution was saturated with oxygen gas. The radical formation chemical reaction competed with nucleophilic addition to the C?N bond of the thiadiazoles. A possible reaction mechanism, and a common reaction intermediate, supported by density functional theory calculations, is presented for the most stable radical. Copyright © 2009 John Wiley & Sons, Ltd. |
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| Keywords: | radical anion thiadiazoles organic electrochemistry ESR spectroscopy DFT calculation |
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