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Decomposition reactions of azo compounds, as studied by quantum chemistry methods and the parabolic model

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Decomposition reactions of azoalkanes of different structure were studied by quantum chemistry methods (MP2/6-311++G** calculations) and by the method of three intersecting parabolas (M3IP). The MP2 method was used to obtain the transition-state geometries, the bond lengths in the molecules under study, and the activation energies. Possible mechanisms of decomposition are discussed. Concerted decomposition of branched azoalkanes was shown to be the most probable mechanism of the process. The M3IP method was used to calculate the kinetic and thermodynamic parameters of concerted decomposition of azoalkanes and to determine and evaluate the main factors affecting the activation energy (E). The stabilization energy of the radical being formed in the decomposition reaction is one of the key factors determining the concerted mechanism. The kinetic parameters calculated by the two independent methods are in good agreement.

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Authors and Affiliations

  1. Institute of Problems of Chemical Physics, Russian Academy of Sciences, 1 prosp. Akad. Semenova, 142432, Chernogolovka, Moscow Region, Russian Federation

    T. S. Pokidova & N. S. Emelyanova

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  1. T. S. Pokidova
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  2. N. S. Emelyanova
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Correspondence to T. S. Pokidova.

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Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 927–933, May, 2022.

This work was carried out as part of the State Assignment under Contract No. AAAA-A19-119071190045-0.

No human or animal subjects were used in this research.

The authors declare no competing interests.

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Pokidova, T.S., Emelyanova, N.S. Decomposition reactions of azo compounds, as studied by quantum chemistry methods and the parabolic model. Russ Chem Bull 71, 927–933 (2022). https://doi.org/10.1007/s11172-022-3492-4

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  • DOI: https://doi.org/10.1007/s11172-022-3492-4

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