Effect of transition state aromaticity and antiaromaticity on intrinsic barriers of proton transfers in aromatic and antiaromatic heterocyclic systems; An ab initio study

Journal of Organic Chemistry

Volumn 75, Issue 24, 2010, Pages 8422-8434

  Bernasconi, Claude F ^a   Wenzel, Philip J ^a  

^a UNIVERSITY OF CALIFORNIA   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

AB INITIO STUDY; ANTIAROMATIC SYSTEMS; ANTIAROMATICITY; AROMATIC STABILIZATION ENERGIES; AROMATIC SYSTEM; AROMATICITIES; CHARGE DELOCALIZATION; CYCLIC SYSTEMS; HETEROCYCLIC SYSTEMS; INTRINSIC BARRIERS; LINEAR REFERENCE SYSTEMS; POLARIZABILITY EFFECTS; PROTON AFFINITY; PROTON TRANSFER REACTIONS; PROTONATED SPECIES; REACTION COORDINATES; REFERENCE SYSTEMS; TRANSITION STATE;

AROMATIC COMPOUNDS; LINEAR SYSTEMS; POLARIZATION; PROTON TRANSFER; REACTION KINETICS; RESONANCE;

AROMATIZATION;

AROMATIC COMPOUND; CARBON; HETEROCYCLIC COMPOUND;

AB INITIO CALCULATION; ARTICLE; CHEMICAL REACTION; PHASE TRANSITION; POLARIZATION; PROTON TRANSPORT;

EID: 78650387997     PISSN: 00223263     EISSN: 15206904     Source Type: Journal    
DOI: 10.1021/jo101719z     Document Type: Article

References (64)

1. 1 ‡ = Δ H -1‡ when Δ H ° = 0
2. Marcus, R. A. J. Phys. Chem. 1968, 72, 891
3. Keeffe, J. R.; Kresge, A. J. In Investigation of Rates and Mechanisms of Reactions; Bernasconi, C. F., Ed.; Wiley-Interscience: New York, 1986; Part 1, p 747.
4. Bernasconi, C. F. Acc. Chem. Res. 1987, 20, 301
5. Bernasconi, C. F. Adv. Phys. Org. Chem. 1992, 27, 119
6. Bernasconi, C. F. Acc. Chem. Res. 1992, 25, 9
7. Bernasconi, C. F. Adv. Phys. Org. Chem. 2010, 44, 223
8. A reactant stabilizing factor that is lost ahead of bond changes increases the intrinsic barrier while a reactant stabilizing factor whose loss lags behind bond changes lowers the intrinsic barrier.
9. For reactant and product de stabilizing factors all the above relations are reversed, e.g., a product destabilizing factor that lags behind bond changes lowers the intrinsic barrier, etc.
10. Bernasconi, C. F.; Sun, W.; García-Río, L.; Kin-Yan; Kittredge, K. J. Am. Chem. Soc. 1997, 119, 5583
11. Bernasconi, C. F.; Kittredge, K. W. J. Org. Chem. 1998, 63, 1944
12. Bernasconi, C. F.; Ali, M. J. Am. Chem. Soc. 1999, 121, 3039
13. Bernasconi, C. F.; Sun, W. J. Am. Chem. Soc. 2002, 124, 2799
14. Bernasconi, C. F.; Ali, M.; Gunter, J. C. J. Am. Chem. Soc. 2003, 125, 151
15. Bernasconi, C. F.; Fairchild, D. E.; Montañez, R. L.; Aleshi, P.; Zheng, H.; Lorance, E. J. Org. Chem. 2005, 70, 7721
16. Bernasconi, C. F.; Ragains, M. L. J. Organomet. Chem. 2005, 690, 5616
17. Bernasconi, C. F.; Pérez-Lorenzo, M.; Brown, S. D. J. Org. Chem. 2007, 72, 4416
18. Terrier, F.; Lelièvre, J.; Chatrousse, A.-P.; Farrell, P. J. Chem. Soc., Perkin Trans. 2 1985, 1479
19. Terrier, F.; Xie, H.-Q.; Lelièvre, J.; Boubaker, T.; Farrell, P. G. J. Chem. Soc., Perkin Trans. 2 1990, 1899
20. Moutiers, G.; El Fahid, B.; Collet, A.-G.; Terrier, F. J. Chem. Soc., Perkin Trans. 2 1996, 49
21. Moutiers, G.; El Fahid, B.; Goumont, R.; Chatrousse, A.-P.; Terrier, F. J. Org. Chem. 1996, 61, 1978
22. Nevy, J. B.; Hawkinson, D. C.; Blotny, G.; Yao, X.; Pollack, R. M. J. Am. Chem. Soc. 1997, 119, 12722
23. Yao, X.; Gold, M.; Pollack., R. M. J. Am. Chem. Soc. 1999, 121, 6220
24. Zhong, Z.; Snowden, T. S.; Best, M. D.; Anslyn, E. V. J. Am. Chem. Soc. 2004, 126, 3488
25. Kresge, A. J. Can. J. Chem. 1974, 52, 1897
26. For earlier important work on solvation, see refs 12 and 13.
27. Cox, B. G.; Gibson, A. Chem. Soc., Faraday Symp. 1975, 10, 107
28. Keeffe, J. R.; Morey, J.; Palmer, C. A.; Lee, J. C. J. Am. Chem. Soc. 1978, 101, 1295
29. Polarizability effects drop off with the fourth power of distance while inductive effects drop off with square of distance. (15)
30. Taft, R. W.; Topsom, R. D. Prog. Phys. Org. Chem. 1987, 119, 7545
31. Bernasconi, C. F.; Ragains, M. L.; Bhattacharya, S. J. Am. Chem. Soc. 2003, 125, 12328
32. Bernasconi, C. F.; Pérez-Lorénzo, M. J. Am. Chem. Soc. 2007, 129, 2704
33. Bernasconi, C. F.; Wenzel, P. J.; Ragains, M. L. J. Am. Chem. Soc. 2008, 130, 4934
34. Bernasconi, C. F.; Yamataka, H.; Yoshimura, N.; Sato, M. J. Org. Chem. 2009, 74, 188
35. Cyránski, M. K. Chem. Rev. 2005, 105, 3773
36. See paragraph concerning Supporting Information at the end of this article.
37. Chesnut, D. B.; Quin, L. D. Heteroatom. Chem. 2004, 18, 754
38. Vessaly, B. J. Struct. Chem. 2008, 49, 979
39. 2) single bonds typically range from 1.45 to 1.48 Å while C=C double bonds typically range from 1.31 to 1.34 Å. (23)
40. Anslyn, E. V.; Dougherty, D. A. Modern Physical Organic Chemistry; University Science Books: Sausalito, CA, 2006; p 22.
41. 3Al is 1.957 Å. (25)
42. Almenningen, A.; Halvorsen, S.; Haaland, A. Acta Chem. Scand. 1971, 25, 1937
43. The B-C bond in trimethyl borane is 1.560 Å. (27)
44. Lévy, H. A.; Brockway, L. O. J. Am. Chem. Soc. 1937, 59, 2085
45. Bernasconi, C. F.; Wenzel, P. J. J. Am. Chem. Soc. 1994, 116, 5405
46. Schleyer, P. v. R.; Maerker, C.; Dransfeld, A.; Jiao, H.; van Eikema Hommes, W. J. R. J. Am. Chem. Soc. 1996, 118, 6317
47. Chen, Z.; Wannese, C. S.; Corminboeuf, C.; Puenta, R.; Schleyer, P. v. R. Chem. Rev. 2005, 105, 3342
48. NICS(1) values determined 1 Å above the ring center have recently been recognized as being a more reliable measures of aromaticity compared to NICS(0) evaluated at the center. (29b)
49. The P-C bond lengths referred to are summarized in Figures S7 and S9 in Supporting Information. (19)
50. The BSSE (basis set superposition error) corrections were estimated by the counterpoise method. (33)
51. Boys, S. F.; Bernardi, F. Mol. Phys. 1970, 19, 553
52. α(SMe) = -0.68 for the polarizability. (35)
53. Hansch, C.; Leo, A.; Taft, R. W. Chem. Rev. 1991, 91, 165
54. Dransfeld, A.; Nyulászc, L.; Schleyer, P. v. R. Inorg. Chem. 1998, 37, 4413
55. Farneth, W. E.; Brauman, J. I. J. Am. Chem. Soc. 1976, 98, 7891
56. Moylan, C. R.; Brauman, J. I. Amer. Rev. Phys. Chem. 1983, 34, 187
57. Bernasconi, C. F.; Ruddat, V.; Wenzel, P. J.; Fisher, H. J. Org. Chem. 2004, 69, 5232
58. Bernasconi, C. F. Pure Appl. Chem. 2009, 81, 651
59. Evans, M. G. Trans. Faraday Soc. 1939, 35, 651
60. Dewar, M. J. S. The Molecular Orbital Theory of Organic Reactions; McGraw-Hill: New York, 1969; pp 316 - 339.
61. Zimmerman, H. Acc. Chem. Res. 1971, 4, 272
62. Frisch, M. J. et al. Gaussian 98, Revision A.7; Gaussian, Inc.: Pittsburgh, PA, 1998.
63. Frisch, M. J. et al. Gaussian 03, Revision D.01; Gaussian, Inc.: Wallingford, CT, 2004.
64. Scott, A.; Radom, L. J. Phys. Chem. 1996, 100, 16502