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BY-NC-ND 3.0 license Open Access Published by De Gruyter Open Access December 16, 2010

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

  • Carolina Estarellas EMAIL logo , Antonio Frontera , David Quiñonero and Pere Deyà
From the journal Open Chemistry


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.

[1] E.A. Meyer, R.K. Castellano, F. Diederich, Angew. Chem. Int. Ed. 42, 1210 (2003) in Google Scholar

[2] A.K. Rappé, E.R. Bernstein, J. Phys. Chem. A 104, 6117 (2000) in Google Scholar

[3] A. Hesselmann, G. Jansen, M. Schütz, J. Am. Chem. Soc. 128, 11730 (2006) in Google Scholar

[4] M. Piacenza, S. Grimme, Chem. Phys. Chem. 6, 1554 (2005) 10.1002/cphc.200500100Search in Google Scholar

[5] J.C. Ma, D.A. Dougherty, Chem. Rev. 97, 1303 (1997) in Google Scholar

[6] J.P. Gallivan, D.A. Dougherty, Proc. Natl. Acad. Sci. USA 96, 9459 (1999) in Google Scholar

[7] G.W. Gokel, S.L.D. Wall, E.S. Meadows, Eur. J. Org. Chem. 2967 (2000) 10.1002/1099-0690(200009)2000:17<2967::AID-EJOC2967>3.0.CO;2-OSearch in Google Scholar

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

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

[10] C.A. Hunter, J. Singh, J.M. Thorton, J. Mol. Biol. 218, 837 (1991) in Google Scholar

[11] H. Ishikita, E.W. Knapp, J. Am. Chem. Soc. 129, 1210 (2007) in Google Scholar

[12] D.A. Dougherty, Science 271, 163 (1996) in Google Scholar

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

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

[15] M. Mascal, A. Armstrong, M.D. Bartberger, J. Am. Chem. Soc. 124, 6274 (2002) in Google Scholar

[16] I. Alkorta, I. Rozas, J. Elguero, J. Am. Chem. Soc. 124, 8593 (2002) in 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)<3389::AID-ANIE3389>3.0.CO;2-S10.1002/1521-3773(20020916)41:18<3389::AID-ANIE3389>3.0.CO;2-SSearch in Google Scholar

[18] M. Egli, S. Sarkhel, Acc. Chem. Res. 40, 197 (2007) in Google Scholar

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

[20] D. Bancroft, L.D. Williams, A. Rich, M. Egli, Biochemistry 33, 1073 (1994) in Google Scholar

[21] S. Sarkhel, A. Rich, M. Egli, J. Am. Chem. Soc. 125, 8998 (2003) in Google Scholar PubMed

[22] J.C. Calabrese, D.B. Jordan, A. Boodhoo, S. Sariaslani, T. Vannelli, Biochemistry, 43, 11403 (2004) in Google Scholar PubMed

[23] T.J. Mooibroek, P. Gamez, J. Reedijk, Cryst Eng Comm 10, 1501 (2008) 10.1039/b812026aSearch in Google Scholar

[24] P. de Hoog, A. Robertazzi, I. Mutikainen, U. Turpeinen, P. Gamez, J. Reedijk, Eur. J. Inorg. Chem. 2684 (2009) 10.1002/ejic.200900183Search in Google Scholar

[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) in Google Scholar PubMed

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

[27] T.J. Mooibroek, S.J. Teat, C. Massera, J. Reedijk, Cryst. Growth Des. 6, 1569 (2006) in Google Scholar

[28] R.F.W. Bader, Chem. Rev. 91, 893 (1991) in Google Scholar

[29] E. Cubero, M. Orozco, F.J. Luque, J. Phys. Chem. A 103, 315 (1999) in Google Scholar

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

[31] F.J. Luque, M. Orozco, J. Comput. Chem. 19, 866 (1998)<866::AID-JCC6>3.0.CO;2-N10.1002/(SICI)1096-987X(199806)19:8<866::AID-JCC6>3.0.CO;2-NSearch in 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) Search in Google Scholar

[33] S.B. Boys, F. Bernardy, Mol. Phys. 19, 553 (1970) in Google Scholar

[34] F. Biegler-König, J. Schönbohm, D. Bayles, J. Comp. Chem. 22, 545 (2001)<545::AID-JCC1027>3.0.CO;2-Y10.1002/1096-987X(20010415)22:5<545::AID-JCC1027>3.0.CO;2-YSearch in Google Scholar

[35] E. Sigfridson, U. Ryde, J. Comput. Chem. 19, 377 (1998)<377::AID-JCC1>3.0.CO;2-P10.1002/(SICI)1096-987X(199803)19:4<377::AID-JCC1>3.0.CO;2-PSearch in Google Scholar

[36] F.J. Luque, M. Orozco, MOPETE computer program (University of Barcelona, Barcelona, 1998) Search in Google Scholar

[37] B. Hernández, M. Orozco, F.J. Luque, J. Comput. Aided Mol. Des. 11, 153 (1997) in Google Scholar

[38] F.J. Luque, M. Orozco, J. Chem. Soc., Perkin Trans. 2, 683 (1993) 10.1039/p29930000683Search in Google Scholar

[39] E. Scrocco, J. Tomasi, Top. Curr. Chem. 42, 95 (1973) Search in Google Scholar

[40] M. Orozco, F.J. Luque, J. Comput. Chem. 14, 587 (1993) in Google Scholar

[41] M.M. Francl, J. Phys. Chem. 89, 428 (1985) in Google Scholar

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

[43] E. Cubero, M. Orozco, F.J. Luque, J. Phys. Chem. A 103, 315 (1999) in 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) in Google Scholar

[45] C. Estarellas, A. Frontera, D. Quiñonero, I. Alkorta, P.M. Deyà, J. Elguero, J. Phys. Chem. A 113, 3266 (2009) in Google Scholar PubMed

[46] F.H. Allen, Acta Crystallogr. B58, 380 (2002) 10.1107/S0108768102003890Search in Google Scholar PubMed

[47] A. Nangia, K. Biradha, G.R. Desiraju, J. Chem. Soc., Perkin Trans. 2, 943 (1996) 10.1039/P29960000943Search in Google Scholar

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

[49] I.I Zviedre, E.M. Shvarts, V.K. Belskii, Zh. Neorg. Khim. 44, 1994 (1999) Search in Google Scholar

Published Online: 2010-12-16
Published in Print: 2011-2-1

© 2011 Versita Warsaw

This work is licensed under the Creative Commons Attribution-NonCommercial-NoDerivatives 3.0 License.

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