Skip to main content
SpringerLink
Log in

Influence of F and CF3 Groups at the C=C Double Bond on the Structure and Properties of Protonated Forms of Olefin‐Series Compounds: an MP2 ab initio Study

  • Published:
Journal of Structural Chemistry Aims and scope Submit manuscript

Abstract

The ab initio MP2 method using the 6−31G* basis set with full geometry optimization was employed to calculate the protonated fluoroolefin molecules (F)i(H)jC=C(F)k(H)l (A) and (CF3)i(F)jC=C(CF3)k×(F)l (B), where i + j = k + l = 2. It is shown that a proton is attached to a carbon atom that is linked to fewer fluorine atoms as substituents. In series A, the proton affinity (PA:rpar; passes through a maximum as the number of fluorine atoms in the molecule increases. The highest PA is found for the 1,1′‐difluoroethylene molecule (182.6 kcal/mole). In series B, the PA decreases monotonically, assuming an anomalously low value for the tetra(trifluoromethyl)ethylene molecule (114.7 kcal/mole). The obtained results are compared with Hartree–Fock calculations; the Hartree–Fock method is inadequate for predicting the structures of the carbocations examined.

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. U. Sheppard and K. Sharts, Organic Fluorine Chemistry, Benjamin-Cuimmings, New York (1969).

    Google Scholar 

  2. K. Zhang, D. M. Zimmerman, A. Chung-Phillips, and C. J. Cassady, J. Amer. Chem. Soc., 115, 10812-10822 (1993).

    Google Scholar 

  3. K. Zhang, C. J. Cassady, and A. Chung-Phillips, J. Amer. Chem. Soc., 116, 11512-11521 (1994).

    Google Scholar 

  4. C. J. Cassady, S. R. Carr, K. Zhang, and A. Chung-Phillips, J. Org. Chem., 60, 1704-1712 (1995).

    Google Scholar 

  5. G. S. Gorman and I. J. Amster, J. Amer. Chem. Soc., 115, 5729-5735 (1993).

    Google Scholar 

  6. S. Cambell, E. M. Marzluff, M. T. Rodgers, et al., J. Amer. Chem. Soc., 116, 5257-5264 (1994).

    Google Scholar 

  7. Yu. A. Borisov and B. C. Harrett, Izv. Ross. Akad. Nauk, Ser. Khim., 9, 1726-1731 (1998).

    Google Scholar 

  8. Yu. A. Borisov, Izv. Ross. Akad. Nauk, Ser. Khim., 11, 1847-1849 (2000).

    Google Scholar 

  9. Yu. A. Borisov, Izv. Akad. Nauk, Ser. Khim., 8, 1333-1337 (2000).

    Google Scholar 

  10. M. J. Frisch, G. W. Trucks, H. B. Schlegel, et. al, GAUSSIAN-98 (Rev. A.5), Gaussian, Inc., Pittsburgh, PA (1998).

    Google Scholar 

  11. E. del Rio, R. Lopez, and T. L. Sordo, J. Phys. Chem. A, 102, 6831-6834 (1998).

    Google Scholar 

  12. Yu. A. Borisov, Zh. Strukt. Khim., 43, No. 5. 794-802 (2002).

    Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Institute of Organoelement Compounds, Russian Academy of Sciences, Moscow

    Yu. A. Borisov

Authors
  1. Yu. A. Borisov
    View author publications

    You can also search for this author in PubMed Google Scholar

Rights and permissions

Reprints and permissions

About this article

Cite this article

Borisov, Y.A. Influence of F and CF3 Groups at the C=C Double Bond on the Structure and Properties of Protonated Forms of Olefin‐Series Compounds: an MP2 ab initio Study. Journal of Structural Chemistry 43, 743–749 (2002). https://doi.org/10.1023/A:1022808820587

Download citation

  • Issue Date:

  • DOI: https://doi.org/10.1023/A:1022808820587

Keywords

Search

Navigation