Research on Chemical Intermediates

, Volume 28, Issue 1, pp 41–48 | Cite as

π -Type and σ -type cation- π complexes of atomic cations

  • Rong Chen
  • Yu-Hui Cheng
  • Lei Liu
  • Xiao-Song Li
  • Qing-Xiang Guo
Article

Abstract

MP2/6-31+G* calculations were performed on the cation-π complexes of ethylene, cyclobutadiene and benzene with a number of atomic cations. It was found that except B+ all the atomic cations form π-type cation-π complexes with ethylene. On the other hand, with cyclobutadiene Li+, N+, Na+, P+ and K+ form π-type complexes, whereas H+, F+, and Cl+ form covalent σ-type complexes. With benzene Li+, B+, Na+, Al+, and K+ form π-type complexes whereas H+, F+, and Cl+ form σ-type complexes. It was concluded that the driving force to form the σ-type complex is chemical bonding, and that for metal cations to form π-type complexes is non-covalent interaction.

cation-pi interaction sigma complex pi complex ab initio 

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REFERENCES

  1. 1.
    J. C. Ma and D. A. Dougherty, Chem. Rev. 97, 1303 (1997).PubMedGoogle Scholar
  2. 2.
    G. W. Gokel, S. L. De Wall and E. S. Meadows, Eur. J. Org. Chem. 2967 (2000).Google Scholar
  3. 3.
    S. M. Hubig and J. K. Kochi, J. Org. Chem. 65, 6807 (2000).PubMedGoogle Scholar
  4. 4.
    K. S. Kim, P. Tarakeshwar and J. Y. Lee, Chem. Rev. 100, 4145 (2000).PubMedGoogle Scholar
  5. 5.
    R. S. Mason, C. M. Williams and P. D. J. Anderson, J. Chem. Soc. Chem. Commun. 1027 (1995).Google Scholar
  6. 6.
    M. N. Glukhovtsev, A. Pross, A. Nicolaides and L. Radom, J. Chem. Soc. Chem. Commun. 2347 (1995).Google Scholar
  7. 7.
    G. Raos, L. Astorri, M. Raimondi, D. L. Cooper, J. Gerratt and P. B. Karadakov, J. Phys. Chem. A 101, 2886 (1997).Google Scholar
  8. 8.
    P. C. Miklis, R. Ditchfield and T. A. Spencer, J. Am. Chem. Soc. 120, 10482 (1998).Google Scholar
  9. 9.
    P. V. R. Schleyer, P. Buzek, T. Muller, Y. Apeloig and H.-U. Siehl, Angew. Chem. Int. Ed. Engl. 32, 1471 (1993).Google Scholar
  10. 10.
    L. Olsson and D. Cremer, Chem. Phys. Lett. 215, 433 (1993).Google Scholar
  11. 11.
    M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, A. Robb, J. R. Cheeseman, V. G. Zakrzewski, J. A. Montgomery, Jr., R. E. Stratmann, J. C. Burant, S. Dapprich, J. M. Millam, A. D. Daniels, K. N. Kudin, M. C. Strain, O. Farkas, J. Tomasi, V. Barone, M. Cossi, R. Cammi, B. Mennucci, C. Pomelli, C. Adamo, S. Clifford, J. Ochterski, G. A. Petersson, P. Y. Ayala, Q. Cui, K. Morokuma, D. K. Malick, A. D. Rabuck, K. Raghavachari, J. B. Foresman, J. Cioslowski, J. V. Ortiz, A. G. Baboul, B. B. Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R. Gomperts, R. L. Martin, D. J. Fox, T. Keith, M. A. Al-Laham, C. Y. Peng, A. Nanayakkara, C. Gonzalez, M. Challacombe, P. M. W. Gill, B. Johnson, W. Chen, M. W. Wong, J. L. Andres, C. Gonzalez, M. Head-Gordon, E. S. Replogle and J. A. Pople, Gaussian 98, Revision A.7. Gaussian, Inc., Pittsburgh, PA (1998).Google Scholar
  12. 12.
    G. W. Wheland, J. Am. Chem. Soc. 64, 900 (1942).Google Scholar
  13. 13.
    S. F. Boys and F. Bernardi, Mol. Phys. 19, 553 (1970).Google Scholar
  14. 14.
    Z. B. Maksic, B. Kovacevic and A. Lesar, Chem. Phys. 253, 59 (2000).Google Scholar
  15. 15.
    J. B. Nicholas, B. P. Hay and D. A. Dixon, J. Phys. Chem. A 103, 1394 (1999).Google Scholar
  16. 16.
    R. C. Dunbar, S. J. Klippenstein, J. Hrusak, D. Stockigt and H. Schwarz, J. Am. Chem. Soc. 118, 5277 (1996).Google Scholar
  17. 17.
    Y. Osamura, K. Terada, Y. Kobayashi, R. Okazaki and Y. Ishiyama, J. Mol. Struct. (THEOCHEM) 462, 399 (1999).Google Scholar
  18. 18.
    M. W. Wong, J. Naker, R. H. Nobes and L. Radom, J. Am. Chem. Soc. 109, 2245 (1987).Google Scholar
  19. 19.
    T. P. Hamilton and H. F. Schaefer, III, J. Am. Chem. Soc. 112, 8260 (1990).Google Scholar

Copyright information

© VSP 2002 2002

Authors and Affiliations

  • Rong Chen
  • Yu-Hui Cheng
  • Lei Liu
  • Xiao-Song Li
  • Qing-Xiang Guo

There are no affiliations available

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