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Photochemical transformations of 1,3,5-trioxane radical cations in freonic matrices at 77 K

  • Photochemistry
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Abstract

It was found that the principal photochemical reaction of 1,3,5-trioxane radical cations in freonic matrices at 77 K is their cycle-opening dissociation yielding the distonic radical cation in which the unpaired electron is preferentially localized on the oxygen atom. The dissociation of the trioxane radical cations at 77 K is characterized by high quantum yields, which vary from 0.24 to 0.36 in different matrices. The distonic radical cations produced during photolysis are unstable at 77 K and undergo further transformations, which occur at different rates in freonic matrices. The structure of the intermediates produced and a possible mechanism of the processes are discussed with the use of quantum-chemical calculation data.

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Authors and Affiliations

  1. Moscow State University, Leninskie gory, Moscow, 119992, Russia

    E. A. Belokon’, V. N. Belevskii, E. N. Golubeva, V. I. Pergushov & M. Ya. Mel’nikov

  2. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Leninskii pr. 47, Moscow, 119991, Russia

    M. P. Egorov

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  1. E. A. Belokon’
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  2. V. N. Belevskii
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  3. E. N. Golubeva
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  4. V. I. Pergushov
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  5. M. P. Egorov
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  6. M. Ya. Mel’nikov
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Original Russian Text © E.A. Belokon’, V.N. Belevskii, E.N. Golubeva, V.I. Pergushov, M.P. Egorov, M.Ya. Mel’nikov, 2006, published in Khimiya Vysokikh Energii, 2006, Vol. 40, No. 4, pp. 303–310.

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Belokon’, E.A., Belevskii, V.N., Golubeva, E.N. et al. Photochemical transformations of 1,3,5-trioxane radical cations in freonic matrices at 77 K. High Energy Chem 40, 259–266 (2006). https://doi.org/10.1134/S0018143906040102

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  • DOI: https://doi.org/10.1134/S0018143906040102

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