Temperature dependence of EPR spectrum of 2-trifluoromethylnitrobenzene radical anion in acetonitrile |
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| Authors: | E. A. Polenov L. A. Shundrin P. V. Mel’nikov |
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| Affiliation: | (1) M. V. Lomonosov Moscow State Academy of Fine Chemical Technology, 86 prosp. Vernadskogo, 119571 Moscow, Russian Federation;(2) N. N. Vorozhtsov Novosibirsk Institute of Organic Chemistry, Siberian Branch of the Russian Academy of Sciences, 9 prosp. Akad. Lavrent’eva, 630090 Novosibirsk, Russian Federation |
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| Abstract: | Temperature dependence of the EPR spectrum of 2-trifluoromethylnitrobenzene radical anion in anhydrous acetonitrile in the temperature range 217 K ≤ T ≤ 296 K was studied and simulated. Temperature-dependent dynamic modulation of the fluorine isotropic hyperfine structure is caused by slow hindered rotation of CF3 group with an activation energy of E F* = 36.5±0.5 kJ mol−1, which is the highest value for motions in π-type free radicals studied to date. Dedicated to the memory of Academician V. A. Koptyug on the occasion of the 75th anniversary of his birth. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 926–931, June, 2006. |
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| Keywords: | radical anions isotropic hyperfine interaction dynamic modulation activation parameters hindered rotation slow exchange EPR spectroscopy |
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