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STRUCTURAL ASPECTS OF trans–cis ISOMERIZATION OF AZOBENZENE, 4,4′-AZOPYRIDINE, AND AZOXYBENZENE

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Abstract

Processes of trans–cis isomerization of azobenzene (AZB), 4,4′-azopyridine (AZP), and azoxybenzene (AZOB) are studied using quantum chemical calculations at the DFT/B3LYP/cc-pvTZ level of theory. The chosen objects can serve as reference points when studying intramolecular rearrangements of numerous compounds containing an azo group and an azoxy bridging group. Geometric and electronic characteristics of trans and cis isomers AZB and AZP and four AZOB isomers, as well as transition states (TSs) between them, are determined. It is established that two AZOB isomers containing a semi-polar bond N→O have a significantly lower energy than two isomers with a cyclic NON bridging group. The transition between the low-energy trans–cis isomers proceeds via a TS while preserving the N→O bond so that the oxygen atom does not migrate between the nitrogen atoms. The NBO analysis of the electronic structure is performed, the factors stabilizing the obtained geometric configurations of all isomers and transition states are determined.

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Funding

The statement of the problem and quantum chemical calculations of trans–cis isomerization were funded by the Ministry of Education and Science of the Russian Federation (project No. FZZM-2020-0006).

The NBO calculations were funded by RFBR (project number 19-33-90046) using the computing resources of the Shared Research Center of ISUCT (with the support of the Ministry of Education and Science of the Russian Federation, agreement No. 075-15-2021-671).

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Authors and Affiliations

  1. Ivanovo State University, Ivanovo, Russia

    N. I. Giricheva & M. S. Fedorov

  2. Krestov Institute of Solution Chemistry, Russian Academy of Sciences, Ivanovo, Russia

    I. S. Lebedev

  3. Ivanovo State University of Chemistry and Technology, Ivanovo, Russia

    K. E. Bubnova & G. V. Girichev

Authors
  1. N. I. Giricheva
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  2. I. S. Lebedev
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  3. M. S. Fedorov
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  4. K. E. Bubnova
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  5. G. V. Girichev
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Correspondence to N. I. Giricheva.

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Russian Text © The Author(s), 2021, published in Zhurnal Strukturnoi Khimii, 2021, Vol. 62, No. 12, pp. 2097-2108.https://doi.org/10.26902/JSC_id87024

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Giricheva, N.I., Lebedev, I.S., Fedorov, M.S. et al. STRUCTURAL ASPECTS OF trans–cis ISOMERIZATION OF AZOBENZENE, 4,4′-AZOPYRIDINE, AND AZOXYBENZENE. J Struct Chem 62, 1976–1987 (2021). https://doi.org/10.1134/S0022476621120179

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  • DOI: https://doi.org/10.1134/S0022476621120179

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