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I. D. Sorokin, O. I. Gromov, V. I. Pergushov, D. A. Pomogailo, M. Ya. Melnikov
Photochemistry of 2,2-dimethyl and
2,2,3-trimethyloxirane radical cations in freon matrices at 77 K
Abstract
The nature of radical cations (RCs)
stabilized in irradiated frozen solutions of 2,2-dimethyl- and 2,2,3-trimethyloxirane
in Freons (CFCl3, CF3CCl3) was determined by
means of EPR and UV/Vis spectroscopy as well as quantum chemistry.Itwasestablishedthattheaffordedring-openRCs, formedupon C–Cbondcleavageinthe oxirane ring, undergo intramolecular
hydrogen atom transfer upon the action of light, resulting in the formation of
distonic RCs.
Key words: radicalcations, EPRspectroscopy, photochemistry,
2,2-dimethyloxirane, 2,2,3-trimethyloxirane, matrixstabilization, hydrogen atom transfer, density functional theory.
Copyright (C) Chemistry Dept., Moscow State University, 2002
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