Skip to main content
SpringerLink
Log in

Syntheses based on the electrogeneration of carbenes. 6. Thermodynamics of the formation of carbenes from the anions of chloro- and bromomethanes

  • Physical Chemistry
  • Published:
Bulletin of the Academy of Sciences of the USSR, Division of chemical science Aims and scope

Conclusions

  1. 1.

    We have calculated the heat effects of the reactions which generate methylenes and the halogenocarbenes:CH2, CHCl, CCl2,:CHBr,:CBr2 from the corresponding anions in the gas phase and in solution. It is found that in the gas phase these reactions are thermo-dynamically unfavorable, but that solvation facilitates their occurrence, this effect increasing with increasing polarity of the solvent and with an increase in the number of halogen atoms in the original anion.

  2. 2.

    Interaction with small counterions, modelled as point charges, can increase the heat effect of the reactions investigated.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

Literature cited

  1. M. E. Niyazymbetov, V. A. Petrosyan, A. A. Fainzil'berg, et al., Izv. Akad. Nauk SSSR, Ser. Khim., No. 5, 1094 (1989).

    Google Scholar 

  2. M. Makosha and M. Fedoryn'ski, Zh. Vses. Khim. Ova,24, 466 (1979).

    Google Scholar 

  3. V. A. Petrosyan, M. E. Niyazymbetov, and T. K. Baryshnikova, Izv. Akad. Nauk SSSR, Ser. Khim., No. 1, p. 91 (1988).

    Google Scholar 

  4. V. N. Kondrat'ev (ed.), Bond Energies, Ionization Potentials and Electron Affinities [in Russian], Nauka, Moscow (1974).

    Google Scholar 

  5. M. J. S. Dewar and W. Thiel, J. Am. Chem. Soc.,99, 4899 (1977).

    Google Scholar 

  6. M. J. S. Dewar and E. Healy, J. Comput. Chem.,4, 542 (1983).

    Google Scholar 

  7. K. Ya. Burshtein, Zh. Strukt. Khim.,28, No. 2, 3 (1987).

    Google Scholar 

  8. K. Ya. Burshtein, J. Mol. Struct. Theochem.,153, 195, 203, 209 (1987).

    Google Scholar 

  9. C. W. Bauschicker, J. Chem. Phys.,85, 6510 (1986).

    Google Scholar 

  10. M. J. S. Dewar, and H. S. Rzepa, J. Am. Chem. Soc.,100, 784 (1978).

    Google Scholar 

  11. Short Handbook of Physicochemical Quantities [in Russian], Khimiya, Leningrad (1983).

Download references

Author information

Authors and Affiliations

  1. N. D. Zelinskii Institute of Organic Chemistry, Academy of Sciences of the USSR, Moscow

    I. A. Machkarovskaya, K. Ya. Burshtein & V. A. Petrosyan

Authors
  1. I. A. Machkarovskaya
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. K. Ya. Burshtein
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. V. A. Petrosyan
    View author publications

    You can also search for this author in PubMed Google Scholar

Additional information

For previous communication, see [1].

Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 6, pp. 1304–1309, June, 1989.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Machkarovskaya, I.A., Burshtein, K.Y. & Petrosyan, V.A. Syntheses based on the electrogeneration of carbenes. 6. Thermodynamics of the formation of carbenes from the anions of chloro- and bromomethanes. Russ Chem Bull 38, 1188–1192 (1989). https://doi.org/10.1007/BF00957151

Download citation

  • Received:

  • Issue Date:

  • DOI: https://doi.org/10.1007/BF00957151

Keywords

Search

Navigation