Radiation Chemistry of Organic Molecules in Solid Rare Gas Matrices: 2. Selective Deprotonation of the Primary Radical Cations upon Irradiation of Oxygen-Containing Molecules in Xenon Matrices

The composition of radical products trapped after irradiation of various ethers (dimethyl ether, tetrahydrofuran, methylal, 1,3-dioxolane) or acetaldehyde in xenon matrices at 15–17 K in the presence of electron scavengers was studied by an ESR technique. It was shown that the primary radical cations give corresponding deprotonation products (carbon-centered radicals), rather than stabilize in xenon, under the given experimental conditions. The deprotonation process is characterized by extremely high selectivity; i.e., the only type of radicals resulting from deprotonation at maximum spin density position was observed in each of the cases. The possible mechanism of the reactions and the nature of their selectivity are discussed.