Cation-π interactions in simple aromatics: Electrostatics provide a predictive tool

Journal of the American Chemical Society

Volumn 118, Issue 9, 1996, Pages 2307-2308

  Mecozzi, Sandro ^a   West Jr , Anthony P ^a   Dougherty, Dennis A ^a  

^a California Institute of Technology ^*  (United States)

Author keywords

[No Author keywords available]

Indexed keywords

AROMATIC COMPOUND;

ARTICLE; COMPUTER SIMULATION; DRUG STRUCTURE; MOLECULAR DYNAMICS;

EID: 0029967521     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja9539608     Document Type: Article

References (28)

1. Dougherty, D. A. Science 1996, 271, 163-168.
2. For experimental data and other calculations on cation-π interactions, see: (a) Sunner, J.; Nishizawa, K.; Kebarle, P. J. Phys. Chem. 1981, 85, 1814-1820. (b) Taft, R. W.; Anvia, F.; Gal, J.-F.; Walsh, S.; Capon, M.; Holmes, M. C.; Hosn, K.; Oloumi, G.; Vasanwala, R.; Yazdani, S. Pure Appl. Chem. 1990, 62, 17-23. (c) Guo, B. C.; Purnell, J. W.; Castleman, A. W., Jr. Chem. Phys. Lett. 1990, 168, 155-160. (d) Deakyne, C. A.; Meot-Ner (Mautner), M. J. Am. Chem. Soc. 1985, 107, 474-479. (e) Meot-Ner (Mautner), M.; Deakyne, C. A. J. Am. Chem. Soc. 1985, 107, 469-474. (f) Kim, K. S.; Lee, J. Y.; Lee, S. J.; Ha, T-K.; Kim, D. H. J. Am. Chem. Soc. 1994, 116, 7399-7400. (g) Lee, J. Y.; Lee, S. J.; Choi, H. S.; Cho, S. J.; Kim, K. S.; Ha, T.-K. Chem. Phys. Lett. 1995, 232, 67-71. (h) Mavri, J.; Koller, J.; Hadzi, D. J. Mol. Struct. (Theochem) 1993, 283, 305-312. (i) Basch, H.; Stevens, W. J. Theochem 1995, 338, 305.
3. For experimental data and other calculations on cation-π interactions, see: (a) Sunner, J.; Nishizawa, K.; Kebarle, P. J. Phys. Chem. 1981, 85, 1814-1820. (b) Taft, R. W.; Anvia, F.; Gal, J.-F.; Walsh, S.; Capon, M.; Holmes, M. C.; Hosn, K.; Oloumi, G.; Vasanwala, R.; Yazdani, S. Pure Appl. Chem. 1990, 62, 17-23. (c) Guo, B. C.; Purnell, J. W.; Castleman, A. W., Jr. Chem. Phys. Lett. 1990, 168, 155-160. (d) Deakyne, C. A.; Meot-Ner (Mautner), M. J. Am. Chem. Soc. 1985, 107, 474-479. (e) Meot-Ner (Mautner), M.; Deakyne, C. A. J. Am. Chem. Soc. 1985, 107, 469-474. (f) Kim, K. S.; Lee, J. Y.; Lee, S. J.; Ha, T-K.; Kim, D. H. J. Am. Chem. Soc. 1994, 116, 7399-7400. (g) Lee, J. Y.; Lee, S. J.; Choi, H. S.; Cho, S. J.; Kim, K. S.; Ha, T.-K. Chem. Phys. Lett. 1995, 232, 67-71. (h) Mavri, J.; Koller, J.; Hadzi, D. J. Mol. Struct. (Theochem) 1993, 283, 305-312. (i) Basch, H.; Stevens, W. J. Theochem 1995, 338, 305.
4. For experimental data and other calculations on cation-π interactions, see: (a) Sunner, J.; Nishizawa, K.; Kebarle, P. J. Phys. Chem. 1981, 85, 1814-1820. (b) Taft, R. W.; Anvia, F.; Gal, J.-F.; Walsh, S.; Capon, M.; Holmes, M. C.; Hosn, K.; Oloumi, G.; Vasanwala, R.; Yazdani, S. Pure Appl. Chem. 1990, 62, 17-23. (c) Guo, B. C.; Purnell, J. W.; Castleman, A. W., Jr. Chem. Phys. Lett. 1990, 168, 155-160. (d) Deakyne, C. A.; Meot-Ner (Mautner), M. J. Am. Chem. Soc. 1985, 107, 474-479. (e) Meot-Ner (Mautner), M.; Deakyne, C. A. J. Am. Chem. Soc. 1985, 107, 469-474. (f) Kim, K. S.; Lee, J. Y.; Lee, S. J.; Ha, T-K.; Kim, D. H. J. Am. Chem. Soc. 1994, 116, 7399-7400. (g) Lee, J. Y.; Lee, S. J.; Choi, H. S.; Cho, S. J.; Kim, K. S.; Ha, T.-K. Chem. Phys. Lett. 1995, 232, 67-71. (h) Mavri, J.; Koller, J.; Hadzi, D. J. Mol. Struct. (Theochem) 1993, 283, 305-312. (i) Basch, H.; Stevens, W. J. Theochem 1995, 338, 305.
5. For experimental data and other calculations on cation-π interactions, see: (a) Sunner, J.; Nishizawa, K.; Kebarle, P. J. Phys. Chem. 1981, 85, 1814-1820. (b) Taft, R. W.; Anvia, F.; Gal, J.-F.; Walsh, S.; Capon, M.; Holmes, M. C.; Hosn, K.; Oloumi, G.; Vasanwala, R.; Yazdani, S. Pure Appl. Chem. 1990, 62, 17-23. (c) Guo, B. C.; Purnell, J. W.; Castleman, A. W., Jr. Chem. Phys. Lett. 1990, 168, 155-160. (d) Deakyne, C. A.; Meot-Ner (Mautner), M. J. Am. Chem. Soc. 1985, 107, 474-479. (e) Meot-Ner (Mautner), M.; Deakyne, C. A. J. Am. Chem. Soc. 1985, 107, 469-474. (f) Kim, K. S.; Lee, J. Y.; Lee, S. J.; Ha, T-K.; Kim, D. H. J. Am. Chem. Soc. 1994, 116, 7399-7400. (g) Lee, J. Y.; Lee, S. J.; Choi, H. S.; Cho, S. J.; Kim, K. S.; Ha, T.-K. Chem. Phys. Lett. 1995, 232, 67-71. (h) Mavri, J.; Koller, J.; Hadzi, D. J. Mol. Struct. (Theochem) 1993, 283, 305-312. (i) Basch, H.; Stevens, W. J. Theochem 1995, 338, 305.
6. For experimental data and other calculations on cation-π interactions, see: (a) Sunner, J.; Nishizawa, K.; Kebarle, P. J. Phys. Chem. 1981, 85, 1814-1820. (b) Taft, R. W.; Anvia, F.; Gal, J.-F.; Walsh, S.; Capon, M.; Holmes, M. C.; Hosn, K.; Oloumi, G.; Vasanwala, R.; Yazdani, S. Pure Appl. Chem. 1990, 62, 17-23. (c) Guo, B. C.; Purnell, J. W.; Castleman, A. W., Jr. Chem. Phys. Lett. 1990, 168, 155-160. (d) Deakyne, C. A.; Meot-Ner (Mautner), M. J. Am. Chem. Soc. 1985, 107, 474-479. (e) Meot-Ner (Mautner), M.; Deakyne, C. A. J. Am. Chem. Soc. 1985, 107, 469-474. (f) Kim, K. S.; Lee, J. Y.; Lee, S. J.; Ha, T-K.; Kim, D. H. J. Am. Chem. Soc. 1994, 116, 7399-7400. (g) Lee, J. Y.; Lee, S. J.; Choi, H. S.; Cho, S. J.; Kim, K. S.; Ha, T.-K. Chem. Phys. Lett. 1995, 232, 67-71. (h) Mavri, J.; Koller, J.; Hadzi, D. J. Mol. Struct. (Theochem) 1993, 283, 305-312. (i) Basch, H.; Stevens, W. J. Theochem 1995, 338, 305.
7. For experimental data and other calculations on cation-π interactions, see: (a) Sunner, J.; Nishizawa, K.; Kebarle, P. J. Phys. Chem. 1981, 85, 1814-1820. (b) Taft, R. W.; Anvia, F.; Gal, J.-F.; Walsh, S.; Capon, M.; Holmes, M. C.; Hosn, K.; Oloumi, G.; Vasanwala, R.; Yazdani, S. Pure Appl. Chem. 1990, 62, 17-23. (c) Guo, B. C.; Purnell, J. W.; Castleman, A. W., Jr. Chem. Phys. Lett. 1990, 168, 155-160. (d) Deakyne, C. A.; Meot-Ner (Mautner), M. J. Am. Chem. Soc. 1985, 107, 474-479. (e) Meot-Ner (Mautner), M.; Deakyne, C. A. J. Am. Chem. Soc. 1985, 107, 469-474. (f) Kim, K. S.; Lee, J. Y.; Lee, S. J.; Ha, T-K.; Kim, D. H. J. Am. Chem. Soc. 1994, 116, 7399-7400. (g) Lee, J. Y.; Lee, S. J.; Choi, H. S.; Cho, S. J.; Kim, K. S.; Ha, T.-K. Chem. Phys. Lett. 1995, 232, 67-71. (h) Mavri, J.; Koller, J.; Hadzi, D. J. Mol. Struct. (Theochem) 1993, 283, 305-312. (i) Basch, H.; Stevens, W. J. Theochem 1995, 338, 305.
8. For experimental data and other calculations on cation-π interactions, see: (a) Sunner, J.; Nishizawa, K.; Kebarle, P. J. Phys. Chem. 1981, 85, 1814-1820. (b) Taft, R. W.; Anvia, F.; Gal, J.-F.; Walsh, S.; Capon, M.; Holmes, M. C.; Hosn, K.; Oloumi, G.; Vasanwala, R.; Yazdani, S. Pure Appl. Chem. 1990, 62, 17-23. (c) Guo, B. C.; Purnell, J. W.; Castleman, A. W., Jr. Chem. Phys. Lett. 1990, 168, 155-160. (d) Deakyne, C. A.; Meot-Ner (Mautner), M. J. Am. Chem. Soc. 1985, 107, 474-479. (e) Meot-Ner (Mautner), M.; Deakyne, C. A. J. Am. Chem. Soc. 1985, 107, 469-474. (f) Kim, K. S.; Lee, J. Y.; Lee, S. J.; Ha, T-K.; Kim, D. H. J. Am. Chem. Soc. 1994, 116, 7399-7400. (g) Lee, J. Y.; Lee, S. J.; Choi, H. S.; Cho, S. J.; Kim, K. S.; Ha, T.-K. Chem. Phys. Lett. 1995, 232, 67-71. (h) Mavri, J.; Koller, J.; Hadzi, D. J. Mol. Struct. (Theochem) 1993, 283, 305-312. (i) Basch, H.; Stevens, W. J. Theochem 1995, 338, 305.
9. For experimental data and other calculations on cation-π interactions, see: (a) Sunner, J.; Nishizawa, K.; Kebarle, P. J. Phys. Chem. 1981, 85, 1814-1820. (b) Taft, R. W.; Anvia, F.; Gal, J.-F.; Walsh, S.; Capon, M.; Holmes, M. C.; Hosn, K.; Oloumi, G.; Vasanwala, R.; Yazdani, S. Pure Appl. Chem. 1990, 62, 17-23. (c) Guo, B. C.; Purnell, J. W.; Castleman, A. W., Jr. Chem. Phys. Lett. 1990, 168, 155-160. (d) Deakyne, C. A.; Meot-Ner (Mautner), M. J. Am. Chem. Soc. 1985, 107, 474-479. (e) Meot-Ner (Mautner), M.; Deakyne, C. A. J. Am. Chem. Soc. 1985, 107, 469-474. (f) Kim, K. S.; Lee, J. Y.; Lee, S. J.; Ha, T-K.; Kim, D. H. J. Am. Chem. Soc. 1994, 116, 7399-7400. (g) Lee, J. Y.; Lee, S. J.; Choi, H. S.; Cho, S. J.; Kim, K. S.; Ha, T.-K. Chem. Phys. Lett. 1995, 232, 67-71. (h) Mavri, J.; Koller, J.; Hadzi, D. J. Mol. Struct. (Theochem) 1993, 283, 305-312. (i) Basch, H.; Stevens, W. J. Theochem 1995, 338, 305.
10. For experimental data and other calculations on cation-π interactions, see: (a) Sunner, J.; Nishizawa, K.; Kebarle, P. J. Phys. Chem. 1981, 85, 1814-1820. (b) Taft, R. W.; Anvia, F.; Gal, J.-F.; Walsh, S.; Capon, M.; Holmes, M. C.; Hosn, K.; Oloumi, G.; Vasanwala, R.; Yazdani, S. Pure Appl. Chem. 1990, 62, 17-23. (c) Guo, B. C.; Purnell, J. W.; Castleman, A. W., Jr. Chem. Phys. Lett. 1990, 168, 155-160. (d) Deakyne, C. A.; Meot-Ner (Mautner), M. J. Am. Chem. Soc. 1985, 107, 474-479. (e) Meot-Ner (Mautner), M.; Deakyne, C. A. J. Am. Chem. Soc. 1985, 107, 469-474. (f) Kim, K. S.; Lee, J. Y.; Lee, S. J.; Ha, T-K.; Kim, D. H. J. Am. Chem. Soc. 1994, 116, 7399-7400. (g) Lee, J. Y.; Lee, S. J.; Choi, H. S.; Cho, S. J.; Kim, K. S.; Ha, T.-K. Chem. Phys. Lett. 1995, 232, 67-71. (h) Mavri, J.; Koller, J.; Hadzi, D. J. Mol. Struct. (Theochem) 1993, 283, 305-312. (i) Basch, H.; Stevens, W. J. Theochem 1995, 338, 305.
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21. The initial structures for the complexes were generated by placing the sodium atom above the ring centroid. In all the complexes, the sodium position and the geometry of the aromatic molecule were then optimized, except for the case of pyridine (6), for which the sodium cation was fixed over the ring and the complex optimized with this constraint. We note that compounds 2-10 also exhibit a secondary binding site for sodium on the heteroatom, and in some cases these heteroatom complexes are more stable than the cation-π complex. Details on these heteroatom complexes will be described elsewhere.
22. Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Gill, P. M. W.; Johnson, B. G.; Wong, M. W.; Foresman, J. B.; Robb, M. A.; Head-Gordon, M.; Replogle, E. S.; Comperts, R.; Andres, J. L.; Raghavachari, K.; Binkley, J. S.; Gonzalez, C.; Martin, R. L.; Fox, D. J.; Defrees, D. J.; Baker, J.; Stewart, J. J. P.; Pople, J. A. Gaussian 92/DFT. Revision F.4: Gaussian, Inc., Pittsburgh, PA 1993.
23. unopt.
24. (a) Brown, H. C.; Okamoto, Y. J. Am. Chem. Soc. 1958, 80, 4979.
25. (b) March, J. Advanced Organic Chemistry. 4th ed.; John Wile & Sons: New York. 1993: p 280.
26. unopt vs BE gives a slope of 1.04 and an intercept of 12.3. with a correlation coefficient of 0.992.
27. Caldwell, J. W.; Kollman, P. A. J. Am. Chem. Soc. 1995, 117, 4177-4178.
28. + group will also contribute to the binding, increasing the apparent importance of polarizability in the binding. Here, we have evaluated only the role of the aromatic in cation-π interactions by choosing a nonpolarizable cation.