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Discrimination of stereoisomers of 2-chlorovinyldichloroarsine and bis(2-chlorovinyl)chloroarsine from the data of negative ion mass spectrometry and quantum-chemical simulation

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Abstract

Chromato–mass spectrometry has been applied to investigate technical lewisite containing α- and β-isomers, each containing the respective stereoisomers. The mass spectra of positive ions of the stereoisomers have been practically identical, whereas substantial differences have been observed in the negative ion mass spectra. Using quantum-chemical simulation at the B3LYP/6-311+G(d,p) level, the relative stability of the isomers, bonds dissociation energy, electron affinity, and ionization energy have been estimated. The formation of characteristic negative ions from the cis-isomer of α-lewisite and their absence for the trans-isomer is shown to be driven by the steric factors affecting the rearrangement processes.

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References

  1. Chemical Warfare Agents: Toxicology and Treatment, Marrs, T.C., Maynard, R.L., and Sidell, F.R., Eds., Blackwell: Wiley, 2007.

  2. Goldman, M. and Dacre, J.C., Reviews of Environmental Contamination and Toxicology, 1989, vol. 110, p. 75.

    Article  CAS  Google Scholar 

  3. Ali-Mattila, E., Siivinen, K., Kenttamaa, H., and Savolahti, P., Int. J. Mass Spectr. Ion Phys., 1983, vol. 47, p. 371.

    Article  CAS  Google Scholar 

  4. Khvostenko, V.I., Mass-spektrometriya otritsatel’nykh ionov v organicheskoi khimii (Mass Spectrometry of the Negative Ions in Organic Chemistry), Moscow: Nauka, 1981.

    Google Scholar 

  5. Mazunov, V.B., Shchukin, P.V., Khatymov, R.V., and Muftakhov, M.V., Mass-Spektrom., 2006, vol. 3, no. 1, p. 11.

    CAS  Google Scholar 

  6. Muftakhov, M.V., Khatymova, L.Z., Khatymov, R.V., and Mazunov, V.B., Proc. of the RAS Ufa Scientific Centre, 2014, no. 4, p. 38.

    Google Scholar 

  7. Khatymov, R.V., Muftakhov, M.V., Schukin, P.V., and Mazunov V.A., Russ. Chem. Bull., 2003, vol. 52, no. 9, p. 1974. DOI: 10.1023/B:RUCB.0000009641.29142.3c.

    Article  CAS  Google Scholar 

  8. Terentyev, B.G., Khatymov, R.V., and Ivaniva, ?.V., Proc. of the RAS Ufa Scientific Centre, 2014, no. 3, p. 86.

    Google Scholar 

  9. NIST Chemistry WebBook, NIST Standard Reference Database Number 69, Linstrom, P.J. and Mallard, W.G., Eds., Gaithersburg: National Institute of Standards and Technology. http://webbooknistgov/chemistry (retrieved 12.02.2015).

  10. Urban, J.J. and von Tersch, R.L., J. Phys. Org. Chem., 1999, vol. 12, p. 95. DOI: 10.1002/(SICI)1099-1395 (199902)12:2<95:: AID-POC91>3.OCO;2-V.

    Article  CAS  Google Scholar 

  11. Kuntsevich, A.D., Golovkov, V.F., Pichkhidze, S.Ya., Shuiskii, G.M., and Krivolapov, Yu.A., Dokl. Akad. Nauk, 1994, vol. 338, no. 6, p. 768.

    Google Scholar 

  12. Smith, J.R., Logan, T.P., Szafraniec, L.L., and Jakubowski, Ed.M., Anal. Lett., 1995, vol. 28, no. 8, p. 1541. DOI: 10.1080/00032719508006412.

    Article  CAS  Google Scholar 

  13. Takhistov, V.V. and Ponomarev, D.A., Organicheskaya mass-spektrometriya (Organic Mass Spectrometry), St. Petersburg: BBM, 2005.

    Google Scholar 

  14. Lebedev, A.T., Morozik, Yu.I., Myasoedov, B.F., Rybal’chenko, I.V., and Fomenko, P.V., Mass-Spektrom., 2007, vol. 4, no. 4, p. 255.

    CAS  Google Scholar 

  15. Khvostenko, O.G. and Tuimedov, G.M., Rapid Commun. Mass Spectr., 2006, vol. 20, p. 3699. DOI: 10.1002/rcm.2792.

    Article  CAS  Google Scholar 

  16. Khatymov, R.V., Tuktarov, R.F., and Muftakhov, M.V., JETP Lett., 2011, vol. 93, no. 8, p. 437. DOI: 10.1134/S002136401108011X.

    Article  CAS  Google Scholar 

  17. Modelli, A. and Burrow, P.D., Phys. Chem. Chem. Phys., 2009, vol. 11, p. 8448. DOI: 10.1039/B908770B.

    Article  CAS  Google Scholar 

  18. Khvostenko, V.I. and Rafikov, S.R., Dokl. Akad. Nauk SSSR, 1975, vol. 220, p. 892.

    CAS  Google Scholar 

  19. Granovsky, A.A., Firefly, Version 8, http://classic. chemmsusu/gran/firefly/indexhtml.

  20. Khursan, S.L., Kvantovaya mekhanika i kvantovaya khimiya (Quantum Mechanics and Quantum Chemistry), Ufa: IP Rayanov, 2005.

    Google Scholar 

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Authors and Affiliations

  1. Institute of Molecule and Crystal Physics, Ufa Research Center of Russian Academy of Sciences, pr. Oktyabrya 151, Ufa, 450075, Russia

    R. V. Khatymov

  2. Timoshenko Military Academy of Radiation, Chemical and Biological Protection, Ministry of Defense of Russian Federation, Kostroma, Russia

    M. V. Ivanova & A. G. Terentyev

  3. 27 Scientific Center of Ministry of Defense of Russian Federation, Moscow, Russia

    I. V. Rybal’chenko

  4. Kostroma State Technological University, Kostroma, Russia

    I. V. Rybal’chenko

Authors
  1. R. V. Khatymov
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  2. M. V. Ivanova
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  3. A. G. Terentyev
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  4. I. V. Rybal’chenko
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Corresponding author

Correspondence to R. V. Khatymov.

Additional information

Original Russian Text © R.V. Khatymov, M.V. Ivanova, A.G. Terentyev, I.V. Rybal’chenko, 2015, published in Zhurnal Obshchei Khimii, 2015, Vol. 85, No. 11, pp. 1855–1863.

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Khatymov, R.V., Ivanova, M.V., Terentyev, A.G. et al. Discrimination of stereoisomers of 2-chlorovinyldichloroarsine and bis(2-chlorovinyl)chloroarsine from the data of negative ion mass spectrometry and quantum-chemical simulation. Russ J Gen Chem 85, 2596–2604 (2015). https://doi.org/10.1134/S1070363215110158

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  • DOI: https://doi.org/10.1134/S1070363215110158

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