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Photochemistry of 2,2-Dimethyl- and 2,2,3-Trimethyloxirane Radical Cations in Freon Matrices at 77 K

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Moscow University Chemistry Bulletin Aims and scope

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. It was established that the afforded ring-open RCs, formed upon C–C bond cleavage in the oxirane ring, undergo intramolecular hydrogen atom transfer upon the action of light, resulting in the formation of distonic RCs.

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Notes

  1. Since narrow multiplet EPR spectra of the 3MO RC stabilized in the low-temperature CFCl3 matrix exhibit a considerable angular dependence, this complicates credible attribution of the initial signal detected in the irradiated 3MO/CFCl3 solutions. However, the position of the absorption maximum belonging to the 3MO RC in the UV/Vis spectra detected in CFCl3 as well as the nature of transformations of the EPR spectra during the photolysis demonstrate that both the radiolysis and the photolysis of the 3MO RC stabilized in the CFCl3 matrix results in the same products as in the CF3CCl3 matrix. Further on, only the results found for the 3MO RC in the low-temperature CF3CCl3 matrix are discussed.

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Funding

This work has been performed as part of budget research topic “Kinetics and mechanisms of photochemical, cryochemical and catalytic processes and the creation of new materials and technologies based on molecularly organized systems” AAAA-A21-121011590090-7 with financial support granted by the Russian Foundation for Basic Research (project no. 19-03-00015) with the use of equipment purchased on behalf of the Development Program of Moscow State University.

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Authors and Affiliations

  1. Department of Chemistry, Moscow State University, 119991, Moscow, Russia

    I. D. Sorokin, O. I. Gromov, V. I. Pergushov, D. A. Pomogailo & M. Ya. Melnikov

  2. Russian Institute for Scientific and Technical Information (VINITI), 125190, Moscow, Russia

    D. A. Pomogailo

Authors
  1. I. D. Sorokin
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  2. O. I. Gromov
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  3. V. I. Pergushov
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  4. D. A. Pomogailo
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  5. M. Ya. Melnikov
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Corresponding author

Correspondence to I. D. Sorokin.

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Sorokin, I.D., Gromov, O.I., Pergushov, V.I. et al. Photochemistry of 2,2-Dimethyl- and 2,2,3-Trimethyloxirane Radical Cations in Freon Matrices at 77 K. Moscow Univ. Chem. Bull. 76, 361–369 (2021). https://doi.org/10.3103/S0027131421060092

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  • DOI: https://doi.org/10.3103/S0027131421060092

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