Migration of Radical States in Crystalline Dimethylglyoxime,
FOREIGN TECHNOLOGY DIV WRIGHT-PATTERSON AFB OHIO
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Elementary reactions of the valence migration in single-crystals of dimethylglyoxime DMG gamma-irradiated at 77K and deuterized dimethylglyoxime-0.0-d2 DMG-0.0-d2 are studied on the E.P.R. spectra of radical pairs over a wide range of temperatures. Values of the elementary rate constants and the magnitudes of isotopic kinetic effects are obtained. It has been shown, that at low temperatures fast reactions of the valence migration of type I can proceed by means of the intro- and intermolecular transfer of hydrogen. The values of the rate constants and isotopic kinetic effects of low-temperature reactions are indicateve of the significant role of the tunnel mechanism in the transfer of the hydrogen atom.
- Organic Chemistry
- Radiation and Nuclear Chemistry