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M. Ya. Melnikov, I. D. Sorokin, O. I. Gromov, V. I. Pergushov, D. A. Pomogailo
Photochemistry of oxirane-derived radical
cations in freonic matrices at 77 K
Abstract
Data on the structure and features for
photochemical reactions of radical cations (RC) derived from various oxiranes
(epoxides) that can be stabilized in Freon matrices at 77 K are
summarized. The nature of the RC and the products of their photochemical transformations
have been determined by means of quantum chemistry, electron paramagnetic
resonance (EPR), and low-temperature optical spectroscopy. For RC, it is shown
that, depending on the structure of the precursor molecule, transitions between
their open and cyclic forms, deprotonation reactions affording C-centered
radicals, and more complex transformations can take place when exposed to
light. Possible explanations of the observed effects are discussed.
Key words: radical cations, oxiranes,
photochemistry, mechanisms of reactions, structure of intermediates.
Copyright (C) Chemistry Dept., Moscow State University, 2002
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