Skip to main content
SpringerLink
Log in

Can lone pair-π and cation-π interactions coexist? A theoretical study

  • Invited Paper
  • Published:
Central European Journal of Chemistry

Abstract

The interplay between two important noncovalent interactions involving different aromatic rings is studied by means of ab initio calculations (MP2/6-31++G**) computing the non-additivity energies. In this study we demonstrate the existence of cooperativity effects when cation-π and lone pair-π interactions coexist in the same system.

These effects are studied theoretically using energetic and geometric features of the complexes. In addition we use Bader’s theory of atoms-in-molecules and Molecular Interaction Potential with polarization (MIPp) partition scheme to characterize the interactions. Experimental evidence for this combination of interactions has been obtained from the Cambridge Structural Database.

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. E.A. Meyer, R.K. Castellano, F. Diederich, Angew. Chem. Int. Ed. 42, 1210 (2003)

    Article  CAS  Google Scholar 

  2. A.K. Rappé, E.R. Bernstein, J. Phys. Chem. A 104, 6117 (2000)

    Article  Google Scholar 

  3. A. Hesselmann, G. Jansen, M. Schütz, J. Am. Chem. Soc. 128, 11730 (2006)

    Article  CAS  Google Scholar 

  4. M. Piacenza, S. Grimme, Chem. Phys. Chem. 6, 1554 (2005)

    CAS  Google Scholar 

  5. J.C. Ma, D.A. Dougherty, Chem. Rev. 97, 1303 (1997)

    Article  CAS  Google Scholar 

  6. J.P. Gallivan, D.A. Dougherty, Proc. Natl. Acad. Sci. USA 96, 9459 (1999)

    Article  CAS  Google Scholar 

  7. G.W. Gokel, S.L.D. Wall, E.S. Meadows, Eur. J. Org. Chem. 2967 (2000)

  8. G.W. Gokel, L.J. Barbour, S.L.D. Wall, E.S. Meadows, Coord. Chem. Rev. 222, 127 (2001)

    Article  CAS  Google Scholar 

  9. G.W. Gokel, L.J. Barbour, R. Ferdani, J. Hu, Acc. Chem. Res. 35, 878 (2002)

    Article  CAS  Google Scholar 

  10. C.A. Hunter, J. Singh, J.M. Thorton, J. Mol. Biol. 218, 837 (1991)

    Article  CAS  Google Scholar 

  11. H. Ishikita, E.W. Knapp, J. Am. Chem. Soc. 129, 1210 (2007)

    Article  CAS  Google Scholar 

  12. D.A. Dougherty, Science 271, 163 (1996)

    Article  CAS  Google Scholar 

  13. S.C.R. Lummis, D.L. Beene, N.J. Harrison, H.A. Lester, D.A. Dougherty, Chem. Biol. 12, 993 (2005)

    Article  CAS  Google Scholar 

  14. E. Cubero, F.J. Luque, M. Orozco, Proc. Natl. Acad. Sci. USA 95, 5976 (1998)

    Article  CAS  Google Scholar 

  15. M. Mascal, A. Armstrong, M.D. Bartberger, J. Am. Chem. Soc. 124, 6274 (2002)

    Article  CAS  Google Scholar 

  16. I. Alkorta, I. Rozas, J. Elguero, J. Am. Chem. Soc. 124, 8593 (2002)

    Article  CAS  Google Scholar 

  17. D. Quiñonero, C. Garau, C. Rotger, A. Frontera, P. Ballester, A. Costa, P.M. Deyà, Angew. Chem. Int. Ed. 41, 3389 (2002)

    Article  Google Scholar 

  18. M. Egli, S. Sarkhel, Acc. Chem. Res. 40, 197 (2007)

    Article  CAS  Google Scholar 

  19. M. Egli, R.V. Gessner, Proc. Natl. Acad. Sci. U.S.A. 92, 180 (1995)

    Article  CAS  Google Scholar 

  20. D. Bancroft, L.D. Williams, A. Rich, M. Egli, Biochemistry 33, 1073 (1994)

    Article  CAS  Google Scholar 

  21. S. Sarkhel, A. Rich, M. Egli, J. Am. Chem. Soc. 125, 8998 (2003)

    Article  CAS  Google Scholar 

  22. J.C. Calabrese, D.B. Jordan, A. Boodhoo, S. Sariaslani, T. Vannelli, Biochemistry, 43, 11403 (2004)

    Article  CAS  Google Scholar 

  23. T.J. Mooibroek, P. Gamez, J. Reedijk, Cryst Eng Comm 10, 1501 (2008)

    CAS  Google Scholar 

  24. P. de Hoog, A. Robertazzi, I. Mutikainen, U. Turpeinen, P. Gamez, J. Reedijk, Eur. J. Inorg. Chem. 2684 (2009)

  25. P.J. Kitson, Y.F. Song, P. Gamez, P. de Hoog, D.L. Long, A.D.C. Parenty, J. Reedijk, L. Cronin, Inorg. Chem. 47, 1883 (2008)

    Article  CAS  Google Scholar 

  26. Z.L. Lu, P. Gamez, I. Mutikainen, U. Turpeinen, J. Reedijk, Cryst. Growth Des. 7, 1669 (2007)

    Article  CAS  Google Scholar 

  27. T.J. Mooibroek, S.J. Teat, C. Massera, J. Reedijk, Cryst. Growth Des. 6, 1569 (2006)

    Article  CAS  Google Scholar 

  28. R.F.W. Bader, Chem. Rev. 91, 893 (1991)

    Article  CAS  Google Scholar 

  29. E. Cubero, M. Orozco, F.J. Luque, J. Phys. Chem. A 103, 315 (1999)

    Article  CAS  Google Scholar 

  30. I. Alkorta, F. Blanco, P.M. Deya, J. Elguero, C. Estarellas, A. Frontera, D. Quiñonero, Theor. Chem. Acc. 126, 1 (2010)

    Article  CAS  Google Scholar 

  31. F.J. Luque, M. Orozco, J. Comput. Chem. 19, 866 (1998)

    Article  CAS  Google Scholar 

  32. M.J. Frisch, G.W. Trucks, H.B. Schlegel, G.E. Scuseria, M.A. Robb, J.R. Cheeseman, J.A. Montgomery Jr., T. Vreven, K.N. Kudin, J.C. Burant, J.M. Millam, S.S. Iyengar, J. Tomasi, V. Barone, B. Mennucci, M. Cossi, G. Scalmani, N. Rega, G.A. Petersson, H. Nakatsuji, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, M. Klene, X. Li, J.E. Knox, H.P. Hratchian, J.B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R.E. Stratmann, O. Yazyev, A.J. Austin, R. Cammi, C. Pomelli, J.W. Ochterski, P.Y. Ayala, K. Morokuma, G.A. Voth, P. Salvador, J.J. Dannenberg, V.G. Zakrzewski, S. Dapprich, A.D. Daniels, M.C. Strain, O. Farkas, D.K. Malick, A.D. Rabuck, K. Raghavachari, J.B. Foresman, J.V. Ortiz, Q. Cui, A.G. Baboul, S. Clifford, J. Cioslowski, B.B. Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R.L. Martin, D.J. Fox, T. Keith, M.A. Al-Laham, C.Y. Peng, A. Nanayakkara, M. Challacombe, P.M.W. Gill, B. Johnson, W. Chen, M.W. Wong, C. Gonzalez, J.A. Pople, Gaussian-03 (Gaussian, Inc.: Wallingford, CT, 2003)

    Google Scholar 

  33. S.B. Boys, F. Bernardy, Mol. Phys. 19, 553 (1970)

    Article  CAS  Google Scholar 

  34. F. Biegler-König, J. Schönbohm, D. Bayles, J. Comp. Chem. 22, 545 (2001)

    Article  Google Scholar 

  35. E. Sigfridson, U. Ryde, J. Comput. Chem. 19, 377 (1998)

    Article  Google Scholar 

  36. F.J. Luque, M. Orozco, MOPETE computer program (University of Barcelona, Barcelona, 1998)

    Google Scholar 

  37. B. Hernández, M. Orozco, F.J. Luque, J. Comput. Aided Mol. Des. 11, 153 (1997)

    Article  Google Scholar 

  38. F.J. Luque, M. Orozco, J. Chem. Soc., Perkin Trans. 2, 683 (1993)

    Google Scholar 

  39. E. Scrocco, J. Tomasi, Top. Curr. Chem. 42, 95 (1973)

    CAS  Google Scholar 

  40. M. Orozco, F.J. Luque, J. Comput. Chem. 14, 587 (1993)

    Article  CAS  Google Scholar 

  41. M.M. Francl, J. Phys. Chem. 89, 428 (1985)

    Article  CAS  Google Scholar 

  42. C. Garau, D. Quiñonero, A. Frontera, P. Ballester, A. Costa, P.M. Deya, Org. Lett. 5, 2227 (2003)

    Article  CAS  Google Scholar 

  43. E. Cubero, M. Orozco, F.J. Luque, J. Phys. Chem. A 103, 315 (1999)

    Article  CAS  Google Scholar 

  44. W. Zhu, X. Tan, J. Shen, X. Luo, F. Cheng, P.C. Mok, R. Ji, K. Chen, H. Jiang, J. Phys. Chem. A 107, 2296 (2003)

    Article  CAS  Google Scholar 

  45. C. Estarellas, A. Frontera, D. Quiñonero, I. Alkorta, P.M. Deyà, J. Elguero, J. Phys. Chem. A 113, 3266 (2009)

    Article  CAS  Google Scholar 

  46. F.H. Allen, Acta Crystallogr. B58, 380 (2002)

    CAS  Google Scholar 

  47. A. Nangia, K. Biradha, G.R. Desiraju, J. Chem. Soc., Perkin Trans. 2, 943 (1996)

    Google Scholar 

  48. J. Yang, B.R. Nelson, J.A. Weil, J.W. Quail, Act. Cryst. Section C 50, 1548 (1994)

    Article  Google Scholar 

  49. I.I Zviedre, E.M. Shvarts, V.K. Belskii, Zh. Neorg. Khim. 44, 1994 (1999)

    CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Department of Chemistry, University of the Balearic Islands, 07122, Palma, Spain

    Carolina Estarellas, Antonio Frontera, David Quiñonero & Pere M. Deyà

Authors
  1. Carolina Estarellas
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Antonio Frontera
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. David Quiñonero
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Pere M. Deyà
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Carolina Estarellas.

About this article

Cite this article

Estarellas, C., Frontera, A., Quiñonero, D. et al. Can lone pair-π and cation-π interactions coexist? A theoretical study. cent.eur.j.chem. 9, 25–34 (2011). https://doi.org/10.2478/s11532-010-0127-7

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.2478/s11532-010-0127-7

Keywords

Search

Navigation