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Ion-molecule reactions and thermal isomerization of tricyclo[4.3.0.0]nona-4,8-diene radical cations to tricyclo[4.2.1.0]nona-2,7-diene radical cations in a γ-irradiated frozen Freon matrix |
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| Authors: | I Yu Shchapin V I Feldman V N Belevskii A V Khoroshutin A A Bobylyova |
| Institution: | a Department of Chemistry, M.V. Lomonosov Moscow State University, Leninskie Gory, Moscow 119899, Russia b Karpov Institute of Physical Chemistry, Vorontchovo pole Str. 10, Moscow 103064, Russia |
| Abstract: | A four-step mechanism of isomerization of tricyclo4.3.0.03,7]nona-4,8-diene radical cations to tricyclo4.2.1.04,9]nona-2,7-diene radical cations in γ-irradiated frozen Freon-113 (CFCl2CF2Cl) matrix was suggested on the basis of ESR data. The rearrangement was found to occur via distonic form of the radical cations with spin and charge separation. Furthermore, it was shown that the primary radical cations abstracts hydrogen atom from methylene group of the parent molecule, whereas distonic radical cations reacts via attachment to the C=C bond at 110–119 K. |
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