Skip to main content
SpringerLink
Log in

A quantum-chemical study of alternative chlorotropic isomerization mechanisms for bis(diethylamino)-chlorophosphonium methylide

  • Published:
Theoretical and Experimental Chemistry Aims and scope

Abstract

The MNDO-PM3 method has been used in the supermolecular approximation to examine alternative mechanisms for the chlorotropic isomerization of unsolvated bis(diethylamino)chlorophosphonium methylide and solvated forms of it containing chloroform of 1∶1 and 1∶2 compositions. It is shown that the most favorable channel for the chlorotropic rearrangement of unsolvated P-chloroylide corresponds to the sigmatropic mechanism. There are effects from specific interactions with the chloroform that make themselves felt in the preferential chlorotropic transformation of the isomers by the dissociation-recombination mechanism, whose activation energy E1∶2 ≠=kcal/mol is comparable with the observed activation barrier for the 1,2-shift of the chlorine atom in the related P-chloroylide.

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

References

  1. R. Appel, M. Huppertz, and A. Westerhaus,Chem. Ber.,116, No. 2, 114–118 (1983).

    CAS  Google Scholar 

  2. V. I. Kal'chenko, V. V. Negrebetskii, R. B. Rudyi, et al.,Zh. Obshch. Khim.,53, No. 4 932–934 (1983).

    Google Scholar 

  3. E. A. Romanenko,Teor. Éksp. Khim.,25, No. 2, 237–240 (1989).

    CAS  Google Scholar 

  4. V. I. Boiko, L. I. Samarai, N. V. Mel'nichenko, et al.,Zh. Obshch. Khim.,66, No. 10, 1715–1719 (1996).

    CAS  Google Scholar 

  5. J. J. P. Steward,QCPE Program MOPAC 6.0 (1990).

  6. E. A. Romanenko, A. P. Marchenko, G. I. Koidan, et al.,Ukr. Khim. Zh.,60, 308–311 (1994).

    CAS  Google Scholar 

  7. A. W. Johnson,Ylides and Imines of Phosphorus, John Wiley and Sons Inc., New York (1993).

    Google Scholar 

  8. P. G. Perkins and J. J. P. Stewart,J. Chem. Soc. Faraday Trans. II,78, No. 2, 285–296 (1982).

    Article  CAS  Google Scholar 

  9. M. Dewar and R. Dogerty,Molecular Orbital Perturbation Theory in Organic Chemistry, [Russian translation], Mir, Moscow (1977), pp. 273, 630.

    Google Scholar 

  10. O. I. Kolodyazhnyi and D. B. Golokhov,Zh. Obshch. Khim.,61, No. 3, 691–694 (1991).

    CAS  Google Scholar 

Download references

Authors
  1. E. A. Romanenko
    View author publications

    You can also search for this author in PubMed Google Scholar

Additional information

Institute for Bioorganic Chemistry and Petroleum Chemistry, National Academy of Sciences of Ukraine, 1 Murmanskaya ul., Kiev 253094, Ukraine. Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 35, No. 4, pp. 215–221, July–August, 1999.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Romanenko, E.A. A quantum-chemical study of alternative chlorotropic isomerization mechanisms for bis(diethylamino)-chlorophosphonium methylide. Theor Exp Chem 35, 198–204 (1999). https://doi.org/10.1007/BF02511515

Download citation

  • Received:

  • Revised:

  • Issue Date:

  • DOI: https://doi.org/10.1007/BF02511515

Keywords

Search

Navigation