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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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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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  1. 1.

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

  2. 2.

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

  3. 3.

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

  4. 4.

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

  5. 5.

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

  6. 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.

  7. 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.

  8. 8.

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

  9. 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. 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.

  11. 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.

  12. 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.

  13. 13.

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

  14. 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.

  15. 15.

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

  16. 16.

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

  17. 17.

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

  18. 18.

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

  19. 19.

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

  20. 20.

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

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Correspondence to R. V. Khatymov.

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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).

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  • lewisite
  • resonance electron-capture negative ion mass spectrometry
  • fragmentation
  • rearrangement
  • dissociation energy