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Phenylaminyl Cations in the Liquid and Gas-Phase Phototransformation of Protonated Azobenzene

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Abstract

Data on the spectroscopy of photoexcitation of trans-to-cis isomerization and fragmentation of protonated trans-azobenzene (ABH+) in an inert gas atmosphere are analyzed. Results from gas-phase isomerization are compared to ones from a liquid-phase reaction in aqueous sulfuric acid that results in the formation of cyclic benzo[c]cinnoline. There is no cyclization upon gas-phase trans-to-cis isomerization in a rarefied nitrogen medium at T = 300 K, due to the high rate of inverse cis-to-trans isomerization. It is shown that transformations in both phases proceed with the participation of phenylaminyl type cations trans- and cis-ABH+, which are chromogens. Photofragmentation of trans-ABH+ in an atmosphere of cryogenically cooled helium (T = 40 K) proceeds with the formation of fragment phenyl and phenyl diazonium cations and the participation of phenyl amine cations. Mechanisms of photofragmentation are proposed, including intermediate acts with the participation of H atoms formed by dissociation of the NH group. A fast attack of H atoms along the phenyl ring bonded to the NH group results in the breaking of the C–N bond, eliminating the possibility of trans-to-cis isomerization in a cryogenic helium atmosphere.

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REFERENCES

  1. P. F. Gordon and P. Gregory, Organic Chemistry in Colour (Springer, Berlin, 1983).

    Google Scholar 

  2. M. S. Scholz, J. N. Bull, J. A. Coughlan, et al., J. Phys. Chem. A 121, 6413 (2017).

    Article  CAS  Google Scholar 

  3. G. Feraud, C. Dedonder-Lardeux, C. Jouvet, and E. Marceca, J. Phys. Chem. A 120, 3897 (2016).

    Article  CAS  Google Scholar 

  4. Yu. A. Mikheev, L. N. Guseva, and Yu. A. Ershov, Russ. J. Phys. Chem. A 89, 224 (2015).

    Article  CAS  Google Scholar 

  5. Yu. A. Mikheev, L. N. Guseva, and Yu. A. Ershov, Russ. J. Phys. Chem. A 89, 2036 (2015).

    Article  CAS  Google Scholar 

  6. Yu. A. Mikheev and Yu. A. Ershov, Russ. J. Phys. Chem. A 93, 1195 (2019).

    Article  CAS  Google Scholar 

  7. Yu. A. Mikheev and Yu. A. Ershov, Russ. J. Phys. Chem. A 93, 1411 (2019).

    Article  CAS  Google Scholar 

  8. Yu. A. Mikheev and Yu. A. Ershov, Russ. J. Phys. Chem. A 93, 2314 (2019).

    Article  CAS  Google Scholar 

  9. Yu. A. Mikheev and Yu. A. Ershov, Russ. J. Phys. Chem. A 92, 1911 (2018).

    Article  CAS  Google Scholar 

  10. E. Streitweiser, Molecular Orbital Theory for Organic Chemists (Wiley, New York, 1962).

    Book  Google Scholar 

  11. K. Higashi, H. Baba, and A. Rembaum, Quantum Organic Chemistry (Wiley-Interscience, New York, 1965).

    Google Scholar 

  12. J. A. Grace and M. C. R. Symons, J. Chem. Soc., 958 (1959).

  13. G. E. Lewis, Org. Chem. 25, 2193 (1960).

    Article  CAS  Google Scholar 

  14. G. E. Lewis, Tetrahedron Lett., No. 9, 12 (1960).

  15. F. Gerson, E. Heilbronner, A. van Veen, and B. M. Wepster, Helv. Chim. Acta 43, 1889 (1960).

    Article  CAS  Google Scholar 

  16. E. F. Caldin, Fast Reactions in Solution (Wiley, New York, 1964).

    Google Scholar 

  17. J. U. Andersen, P. Hvelplund, S. B. Nielsen, et al., Rev. Sci. Instrum. 73, 1284 (2002).

    Article  CAS  Google Scholar 

  18. Wang Xue-Bin and Wang Lai-Sheng, Rev. Sci. Instrum. 79, 073108 (2008).

    Article  Google Scholar 

  19. T. Fujino and T. Tahara, J. Phys. Chem. A 104, 4203 (2000).

    Article  CAS  Google Scholar 

  20. Yu. A. Mikheev and Yu. A. Ershov, Russ. J. Phys. Chem. A 93, 369 (2019).

    Article  CAS  Google Scholar 

  21. S. F. Mason, J. Chem. Soc., 1240 (1959).

  22. Yu. A. Mikheev and Yu. A. Ershov, Russ. J. Phys. Chem. A 92, 1499 (2018).

    Article  CAS  Google Scholar 

  23. Yu. A. Mikheev, L. N. Guseva, and Yu. A. Ershov, Russ. J. Phys. Chem. A 94, 143 (2020).

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Authors and Affiliations

  1. Emanuel Institute of Biochemical Physics, Russian Academy of Sciences, 119334, Moscow, Russia

    Yu. A. Mikheev

  2. Bauman Moscow State Technical University, 105005, Moscow, Russia

    Yu. A. Ershov

Authors
  1. Yu. A. Mikheev
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  2. Yu. A. Ershov
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Correspondence to Yu. A. Mikheev.

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Translated by V. Avdeeva

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Mikheev, Y.A., Ershov, Y.A. Phenylaminyl Cations in the Liquid and Gas-Phase Phototransformation of Protonated Azobenzene. Russ. J. Phys. Chem. 94, 1716–1725 (2020). https://doi.org/10.1134/S0036024420080208

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  • DOI: https://doi.org/10.1134/S0036024420080208

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