Identity proton-transfer reactions from C-H, N-H, and O-H acids. An ab initio, DFT, and CPCM-B3LYP aqueous solvent model study

Journal of the American Chemical Society

Volumn 125, Issue 38, 2003, Pages 11730-11745

  Keeffe, James R ^a   Gronert, Scott ^a   Colvin, Michael E ^b,c   Tran, Ngoc L ^a,b  

^a SAN FRANCISCO STATE UNIVERSITY   (United States)

^b LAWRENCE LIVERMORE NATIONAL LABORATORY   (United States)

^c UNIVERSITY OF CALIFORNIA   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

COMPLEXATION; ENTHALPY; HYDROGEN BONDS; SOLVENTS;

PROTON TRANSFER;

ACIDS;

ACID; CARBON; HYDROGEN; NITROGEN; OXYGEN; SOLVENT;

AB INITIO CALCULATION; ARTICLE; CHEMICAL MODEL; CONJUGATE; CORRELATION ANALYSIS; DENSITY; ELECTRICITY; ENTHALPY; GEOMETRY; KINETICS; PARAMETER; PROTON TRANSPORT;

EID: 0141757417     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja0356683     Document Type: Article

References (86)

1. (a) Lapworth, A.; Hann, A. C. O. J. Chem. Soc. 1902, 1508.
2. (b) Lapworth, A. J. Chem. Soc. 1904, 30.
3. (a) Bell, R. P. Acid-Base Catalysis; Oxford University Press: London, 1941.
4. (b) Bell, R. P. The Proton in Chemistry, 2nd ed.; Cornell University Press: Ithaca, NY, 1973.
5. Eigen, M. Angew. Chem., Int. Ed. Engl. 1964, 3, 1.
6. Bruice, T. C.; Benkovic, S. J. Bioorganic Mechanisms; Benjamin: New York, 1966.
7. Jencks, W. P. Catalysis in Chemistry and Enzymology: McGraw-Hill: New York, 1969.
8. Caldin, E. F., Gold, V., Eds.; Proton-Transfer Reactions; Chapman and Hall: London, 1975.
9. Stewart, R. The Proton - Applications to Organic Chemistry; Academic Press: San Diego, 1985.
10. Keeffe, J. R.; Kresge, A. J. In Investigation of Rates and Mechanisms of Reactions, 4th ed.; Bernasconi, C. F., Ed.; Wiley-Interscience: New York, 1986; Part 1, Chapter XI.
11. (a) Brauman, J. I.; Lieder, C. A.; White, M. J. J. Am. Chem. Soc. 1973, 95, 927.
12. (b) Brauman, J. I.; Farneth, W. E. J. Am. Chem. Soc. 1976, 98, 7891.
13. (c) Han, C.-C.; Brauman, J. I. J. Am. Chem. Soc. 1989, 111, 6491.
14. (d) Bohme, D. K.; Rakshit, A. B.; Mackay, G. I. J. Am. Chem. Soc. 1982, 104, 1100.
15. (e) Moylan, C. R.; Brauman, J. I. Annu. Rev. Phys. Chem. 1983, 34, 187.
16. (f) Bowers, M. T., Ed. Gas-Phase Ion Chemistry; Academic Press: New York, 1979.
17. (g) Taft, R. W.; Topsom, R. D. Prog. Phys. Org. Chem. 1987, 16, 1 and references therein.
18. (h) Brickhouse, M. D.; Squires, R. R. J. Am. Chem. Soc. 1988, 110, 2706.
19. (i) Dodd, J. A.; Baer, S.; Moylan, C. R.; Brauman, J. I. J. Am. Chem. Soc. 1991, 113, 5942.
20. (j) Yamataka, H.; Mustanir, Mishima, M. J. Am. Chem. Soc. 1999, 121, 10223.
21. (k) Bartmess, J. E. In NIST Standard Reference Database Number 69; Mallard, W. G., Linstrom, P. J., Eds.; National Institute of Standards and Technology (http://webbook.nist.gov): Gaithersburg, MD, 1999.
22. (l) Tran, N. L.; Colvin, M. E. J. Mol. Struct. (THEOCHEM) 2000, 532, 127.
23. (a) Scheiner, S. Acc. Chem. Res. 1985, 18, 174; 1994, 27, 402.
24. (a) Scheiner, S. Acc. Chem. Res. 1985, 18, 174; 1994, 27, 402.
25. (b) Wolfe, S.; Hoz, S.; Kim, C.-K.; Yang, K. J. Am. Chem. Soc. 1990, 112, 4186.
26. (c) Gronert, S. Organometallics 1993, 12, 3805.
27. (d) Gronert, S. J. Am. Chem. Soc. 1993, 115, 10258.
28. (e) Reference 9h.
29. (a) Bernasconi, C. F.; Wenzel, P. J. J. Am. Chem. Soc. 1994, 116, 5405.
30. (b) Bernasconi, C. F.; Wenzel, P. J.; Keeffe, J. R.; Gronert, S. J. Am. Chem. Soc. 1997, 119, 4008.
31. (c) Bernasconi, C. F.; Wenzel, P. J. J. Am. Chem. Soc. 2001, 123, 7146.
32. (d) Bernasconi, C. F.; Wenzel, P. J. J. Org. Chem. 2001, 66, 968.
33. (a) Pross, A.; Shaik, S. J. Am. Chem. Soc. 1982, 104, 1129.
34. (b) Saunders, W. H., Jr. J. Am. Chem. Soc. 1994, 116, 5400.
35. (c) Saunders, W. H., Jr.; Van Verth, J. E. J. Org. Chem. 1995, 60, 3452.
36. (d) Van Verth, J. E.; Saunders, W. H., Jr.; Kermis, T. W. Can. J. Chem. 1998, 76, 821.
37. (e) Van Verth, J. E.; Saunders, W. H., Jr. Can. J. Chem. 1999, 77, 810.
38. (f) Harris, N.; Wei, W.; Saunders, W. H., Jr.; Shaik, S. J. Am. Chem. Soc. 2000, 122, 6754.
39. (g) Wei, W.; Shaik, S.; Saunders, W. H., Jr. J. Phys. Chem. A 2002, 106, 11616.
40. See refs 10a, 11c, and 11d for other pertinent references.
41. Bell, R. P.; Goodall, D. M. Proc. R. Soc. A 1966, 294, 273.
42. Davies, M. H.; Robinson, B. H.; Keeffe, J. R. Annu. Rep. A 1973, 123.
43. (a) Kresge, A. J. Chem. Soc. Rev. 1973, 2, 475.
44. (b) Kresge, A. J. Clin. J. Chem. 1974, 52, 1897 and references therein.
45. (c) See also: Albery, W. J.; Bernasconi, C. F.; Kresge, A. J. J. Phys. Org. Chem. 1988, 1, 29.
46. Fukuyama, M.; Flanagan, P. W. K.; Williams, F. T., Jr.; Frainier, L.; Miller, S. A.; Schecter, H. J. Am. Chem. Soc. 1970, 92, 4689.
47. (a) Bordwell, F. G.; Boyle, W. J., Jr. J. Am. Chem. Soc. 1971, 93, 511.
48. (b) Bordwell, F. G.; Boyle, W. J., Jr. J. Am. Chem. Soc. 1972, 94, 3907, Brönsted coefficients for proton-transfer events almost always lie between the limits (0 < α or β < 1). They are commonly taken as rough measures of the progress of the transfer at the transition state: α as reported by a set of acids and β when reported by a set of bases. It is recognized that the approximation can be a crude one. Among other reasons, the transition state of a bimolecular reaction step experiences interactions which do not exist in the separated reactants or products. See also ref 8, sections 4 and 7.2.1, ref 12a, and ref 16b.
49. Reference 2b, Chapter 10. See also ref 16b.
50. Hine, J. Adv. Phys. Org. Chem. 1977, 15, 1.
51. (a) Bernasconi, C. F. Acc. Chem. Res. 1987, 20, 301.
52. (b) Bernasconi, C. F. Acc. Chem. Res. 1992, 25, 9.
53. (c) Bernasconi, C. F. Adv. Phys. Org. Chem. 1992, 27, 119.
54. (a) Keeffe, J. R.; Morey, J.; Palmer, C. A.; Lee, J. C. J. Am. Chem. Soc. 1979, 101, 1295.
55. (b) Keeffe, J. R.; Yrigoyen, L. San Francisco State University, unpublished results.
56. (c) Gandler, J. R.; Saunders, O. L.; Barbosa, R. J. Org. Chem. 1997, 62, 4677.
57. (d) Gandler, J. R.; Bernasconi, C. F. J. Am. Chem. Soc. 1992, 114, 631.
58. (e) Cox, B. G.; Gibson, A. Chem. Commun. 1974, 683.
59. (f) Cox, B. G.; Gibson, A. Chem. Soc. Faraday Symp. 1975, 10, 107.
60. Pauling, L. J. Am. Chem. Soc. 1947, 69, 542. See also ref 23 of: Yoo, H. Y.; Houk, K. N. J. Am. Chem. Soc. 1994, 116, 12047.
61. Pauling, L. J. Am. Chem. Soc. 1947, 69, 542. See also ref 23 of: Yoo, H. Y.; Houk, K. N. J. Am. Chem. Soc. 1994, 116, 12047.
62. References 10d, 11b, 12a, 12f, and 12g. The same picture has been used to explain the relative slowness of carbon-centered nucleophiles and nucleofuges in nucleophilic substitution reactions at saturated carbon: Dedieu, A.; Veillard, A. J. Am. Chem. Soc. 1972, 94, 6730. Bader, R. F. W.; Duke, A.; Messer, R. R. J. Am. Chem. Soc. 1973, 95, 7715. Pellerite, M. J.; Brauman, J. I. J. Am. Chem. Soc. 1983, 105, 2672. Chabinyc, M. L.; Craig, S. L.; Regan, C. K. ; Brauman, J. I. Science 1998, 279, 1882. Cao, W.; Erden, I.; Grow, R. H.; Keeffe, J. R.; Song, J.; Trudell, M. B.; Wadsworth, T. L.; Xu, F.-P.; Zheng, J.-B. Can. J. Chem. 1999, 77, 1009.
63. References 10d, 11b, 12a, 12f, and 12g. The same picture has been used to explain the relative slowness of carbon-centered nucleophiles and nucleofuges in nucleophilic substitution reactions at saturated carbon: Dedieu, A.; Veillard, A. J. Am. Chem. Soc. 1972, 94, 6730. Bader, R. F. W.; Duke, A.; Messer, R. R. J. Am. Chem. Soc. 1973, 95, 7715. Pellerite, M. J.; Brauman, J. I. J. Am. Chem. Soc. 1983, 105, 2672. Chabinyc, M. L.; Craig, S. L.; Regan, C. K. ; Brauman, J. I. Science 1998, 279, 1882. Cao, W.; Erden, I.; Grow, R. H.; Keeffe, J. R.; Song, J.; Trudell, M. B.; Wadsworth, T. L.; Xu, F.-P.; Zheng, J.-B. Can. J. Chem. 1999, 77, 1009.
64. References 10d, 11b, 12a, 12f, and 12g. The same picture has been used to explain the relative slowness of carbon-centered nucleophiles and nucleofuges in nucleophilic substitution reactions at saturated carbon: Dedieu, A.; Veillard, A. J. Am. Chem. Soc. 1972, 94, 6730. Bader, R. F. W.; Duke, A.; Messer, R. R. J. Am. Chem. Soc. 1973, 95, 7715. Pellerite, M. J.; Brauman, J. I. J. Am. Chem. Soc. 1983, 105, 2672. Chabinyc, M. L.; Craig, S. L.; Regan, C. K. ; Brauman, J. I. Science 1998, 279, 1882. Cao, W.; Erden, I.; Grow, R. H.; Keeffe, J. R.; Song, J.; Trudell, M. B.; Wadsworth, T. L.; Xu, F.-P.; Zheng, J.-B. Can. J. Chem. 1999, 77, 1009.
65. References 10d, 11b, 12a, 12f, and 12g. The same picture has been used to explain the relative slowness of carbon-centered nucleophiles and nucleofuges in nucleophilic substitution reactions at saturated carbon: Dedieu, A.; Veillard, A. J. Am. Chem. Soc. 1972, 94, 6730. Bader, R. F. W.; Duke, A.; Messer, R. R. J. Am. Chem. Soc. 1973, 95, 7715. Pellerite, M. J.; Brauman, J. I. J. Am. Chem. Soc. 1983, 105, 2672. Chabinyc, M. L.; Craig, S. L.; Regan, C. K. ; Brauman, J. I. Science 1998, 279, 1882. Cao, W.; Erden, I.; Grow, R. H.; Keeffe, J. R.; Song, J.; Trudell, M. B.; Wadsworth, T. L.; Xu, F.-P.; Zheng, J.-B. Can. J. Chem. 1999, 77, 1009.
66. References 10d, 11b, 12a, 12f, and 12g. The same picture has been used to explain the relative slowness of carbon-centered nucleophiles and nucleofuges in nucleophilic substitution reactions at saturated carbon: Dedieu, A.; Veillard, A. J. Am. Chem. Soc. 1972, 94, 6730. Bader, R. F. W.; Duke, A.; Messer, R. R. J. Am. Chem. Soc. 1973, 95, 7715. Pellerite, M. J.; Brauman, J. I. J. Am. Chem. Soc. 1983, 105, 2672. Chabinyc, M. L.; Craig, S. L.; Regan, C. K. ; Brauman, J. I. Science 1998, 279, 1882. Cao, W.; Erden, I.; Grow, R. H.; Keeffe, J. R.; Song, J.; Trudell, M. B.; Wadsworth, T. L.; Xu, F.-P.; Zheng, J.-B. Can. J. Chem. 1999, 77, 1009.
67. Barone, V.; Cossi, M. J. Phys. Chem. A 1998, 102, 1995.
68. Wavefunction, Inc., 18401 Von Karman Avenue, Suite 370, Irvine, CA 92612.
69. Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Gill, P. M. W.; Johnson, B. G.; Robb, M. A.; Cheeseman, J. R.; Keith, T.; Petersson, G. A.; Montgomery, J. A.; Raghavachari, K.; Al-Laham, M. A.; Zakrzewski, V. G.; Ortiz, J. V.; Foresman, J. B.; Cioslowski, J.; Stefanov, B. B.; Nanayakkara, A.; Challacombe, M.; Peng, C. Y.; Ayala, P. Y.; Chen, W.; Wong, M. W.; Andres, J. L.; Replogle, E. S.; Gomperts, R.; Martin, R. L.; Fox, D. J.; Binkley, J. S.; Defrees, D. J.; Baker, M. J.; Stewart, J. P.; Head-Gordon, M.; Gonzalez, C.; Pople, J. A. Gaussian 94, revision E.2; Gaussian, Inc.; Pittsburgh, PA, 1995.
70. Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Zakrzewski, V. G.; Montgomery, J. A., Jr.; Stratmann, R. E.; Burant, J. C.; Dapprich, S.; Millam, J. M.; Daniels, A. D.; Kudin, K. N.; Strain, M. C.; Farkas, O.; Tomasi, J.; Barone, V.; Cossi, M.; Cammi, R.; Mennucci, B.; Pomelli, C.; Adamo, C.; Clifford, S.; Ochterski, J.; Petersson, G. A.; Ayala, P. Y.; Cui, Q.; Morokuma, K.; Salvador, P.; Dannenberg, J. J.; Malick, D. K.; Rabuck, A. D.; Raghavachari, K.; Foresman, J. B.; Cioslowski, J. ; Ortiz, J. V.; Baboul, A. G.; Stefanov, B. B.; Liu, G.; Liashenko, A.; Piskorz, P.; Komaromi, I.; Gomperts, R.; Martin, R. L.; Fox, D. J.; Keith, T.; Al-Laham, M. A.; Peng, C. Y.; Nanayakkara, A.; Challacombe, M.; Gill, P. M. W.; Johnson, B.; Chen, W.; Wong, M. W.; Andres, J. L.; Gonzalez, C.; Head-Gordon, M.; Replogle, E. S.; Pople, J. A. Gaussian 98, revision A.11; Gaussian, Inc.: Pittsburgh, PA, 2001.
71. See paragraph concerning Supporting Information at the end of this paper.
72. ACID and ΔH‡ values of 0.1 ± 0.6 kcal/mol using data from this work and from refs 11c and 11d. For reactions involving the nonplanar allyl anion and the nonplanar nitromethide anion, we also used MP2 frequencies to obtain ΔH values. The same holds for the other nitroalkane reactions (except for the microhydration reactions) because differences between their calculated ΔH values are small and can be affected by the choice of ZPVE values.
73. Lammertsma, K.; Prasad, B. V. J. Am. Chem. Soc. 1993, 115, 2348.
74. Chabinyc, M. L.; Brauman, J. I. J. Am. Chem. Soc. 2000, 122, 5371.
75. See, however, ref 9j; also see: (a) Cybulski, S. M.; Scheiner, S. J. Am. Chem. Soc. 1987, 109, 4199.
76. (b) Chabinyc, M. L.; Brauman, J. I. J. Am. Chem. Soc. 2000, 122, 8739.
77. (a) McAllister, M. A. Can. J. Chem. 1997, 75, 1195.
78. (b) Chen, J. G.; McAllister, M. A.; Lee, J. K.; Houk, K. N. J. Org. Chem. 1998, 63, 4611 and references therein.
79. Keeffe, J. R.; Kresge, A. J. In The Chemistry of Enamines; Rappoport, Z., Ed.; Wiley-Interscience: New York, 1994; Chapter 19. See also the useful data in: MacCormack, A. C.; McDonnell, C. M.; More OFerrall, R. A.; O'Donoghue, A. C.; Rao, S. N. J. Am. Chem. Soc. 2002, 124, 8575.
80. Keeffe, J. R.; Kresge, A. J. In The Chemistry of Enamines; Rappoport, Z., Ed.; Wiley-Interscience: New York, 1994; Chapter 19. See also the useful data in: MacCormack, A. C.; McDonnell, C. M.; More OFerrall, R. A.; O'Donoghue, A. C.; Rao, S. N. J. Am. Chem. Soc. 2002, 124, 8575.
81. - complex.
82. 2 to 0.970. almost the same as for the identity reactions alone.
83. 2 = 0.90.
84. Dewar, M. J. S.; Zoebisch, E. G.; Healy, E. F.; Stewart, J. J. P. J. Am. Chem. Soc. 1985, 107, 3902.
85. Hansch, C.; Leo, A.; Taft, R. W. Chem. Rev. 1991, 91, 165.
86. α > 0, which raises the barrier.