Russian Chemical Bulletin

, Volume 42, Issue 7, pp 1156–1159 | Cite as

Calculation of the proton affinities of polychlorobenzenes and the activation energies of 1,2-hydrogen shifts in arenonium ions

  • Yu. A. Borisov
  • R. M. Kurbanbaev
Physical Chemistry


The proton affinities of benzene, chlorobenzene and polychlorobenzenes with the common formula C6Cl n H6−n (n=0–6) have been calculated by the AM1 method. The proton affinity averaged over the protonated isomers increases monotonically asn growing from 0 to 5, and then decreases when passing from pentato hexachlorobenzene. The energies of proton addition to the different positions in the polychlorobenzene molecules have been estimated. It has been found that unsubstituted carbon atoms are preferred for proton attack. The positions with the highest proton affinity are the carbon atoms with the largest negative charges. The activation energies of 1,2-hydrogen shifts in arenonium ions of the polychlorobenzenes have been calculated.

Key words

quantum-chemical calculations AM1 method polychlorobenzenes proton affinity 1,2-hydrogen shift arenonium ions activation energy 


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  1. 1.
    V. A. Koptyug,Arenonievye iony. Stroenie i reaktsionnaya sposobnost (Arenonium ions. Structure and reactivity), Nauka, Siberian branch, Novosibirsk, 1983 (in Russian).Google Scholar
  2. 2.
    M. J. S. Dewar, E. G. Zoebisch, E. F. Healy, and J. J. P. Stewart,J. Am. Chem. Soc., 1985,107, 3902.Google Scholar
  3. 3.
    V. I. Vedeneev, L. V. Gurvich, V. N. Kondrat'ev, V. A. Medvedev, and E. L. Frankevich,Energii razryva khimicheskikh svyazei. Potensialy ionizatsii i srodstvo k electronu (Energies of chemical bonds. Ionization potentials and electron affinities), Khimiya, Moscow, 1962 (in Russian).Google Scholar
  4. 4.
    E. L. Mackor, A. Hofstra, and J. H. van der Waals,Trans. Faraday Soc., 1958,54, 66, 186.Google Scholar
  5. 5.
    D. M. Brouwer, E. L. Mackor, and C. Maclean, inCarbonium Ions.,2, Eds. G.A.Olah and P. von Schleyer, R. Wiley-Interscience., 1970, 837.Google Scholar
  6. 6.
    D. M. Brouwer and J. A. Doom,Rec. trav. Chem., 1970,89, 88.Google Scholar
  7. 7.
    D. M. Brouwer,Rec. trav. Chem., 1968,87, 611.Google Scholar
  8. 8.
    E. M. Arnett and J. W. Larsen,J. Am. Chem. Soc., 1969,91, 1438.Google Scholar
  9. 9.
    Yu. A. Borisov, N. I. Raevskii, E. S. Mortikov, V. A. Plakhotnik, and I. I. Leshchiner,Izv. Akad. Nauk, Ser. Khim., 1992, 731 [Bull. Acad. Sci. Div. Chem. Sci., 1992,41, 547].Google Scholar
  10. 10.
    W. J. Hehre and J. A. Pople,J. Am. Chem. Soc., 1972,94, 6901.Google Scholar
  11. 11.
    G. A. Olah, R. H. Schlosberg, D. P. Kelly, and G. D. Mateescu,J. Am. Chem. Soc., 1970,92, 2546.Google Scholar

Copyright information

© Plenum Publishing Corporation 1994

Authors and Affiliations

  • Yu. A. Borisov
    • 1
  • R. M. Kurbanbaev
    • 1
  1. 1.A.N.Nesmeyanov Institute of Organoelement CompoundsRussian Academy of SciencesMoscowRussian Federation

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