Unusual ionic hydrogen bonds: Complexes of acetylides and fluoroform

Journal of the American Chemical Society

Volumn 122, Issue 36, 2000, Pages 8739-8745

  Chabinyc, Michael L ^a   Brauman, John I ^a  

^a STANFORD UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ACETIC ACID DERIVATIVE; DEUTERIUM; FLUOROFORM;

ARTICLE; COMPLEX FORMATION; ENERGY; FOURIER ANALYSIS; FRACTIONATION; HYDROGEN BOND; THERMODYNAMICS;

EID: 0034644428     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja000806z     Document Type: Article

References (75)

1. Hibbert, F.; Emsley, J. In Advances in Physical Organic Chemistry; Bethell, D., Ed.; Academic Press: London, 1990; Vol. 26.
2. Perrin, C. L.; Nielson, J. B. Anna. Rev. Phys. Chem. 1997,48,511-544.
3. Kebarle, P. Annu. Rev. Phys. Chem. 1977, 28, 445-476.
4. Mautner, M. Ace. Chem. Res. 1984, 17, 186-93.
5. Takashima, K.; Riveros, J. M. Mass Spectrom. Rev. 1998,17,409-430.
6. (a) Saunders, W. H. J. Am. Chem. Soc. 1994,116, 3452-3458.
7. (b) Saunders, W. H.; Van Verth, J. E. J. Org. Chem. 1995, 60, 3452-3458.
8. Caldwell, G.; Rozeboom, M. D.; Kiplinger, J. P.; Bartmess, J. E. J. Am. Chem. Soc. 1984, 106, 4660-4667.
9. Meot-Ner, M. J. Am. Chem. Soc. 1988, 110, 3858-3862.
10. Cram, D. J. Fundamentals of Carbanion Chemistry; Academic Press: New York, 1965.
11. Ahlberg, P.; Davidsson, Ö. J. Chem. Soc., Chem. Commun. 1987, 623-624.
12. Chabinyc, M. L.; Brauman, J. I. J. Am. Chem. Soc. 1998, 120, 10863-10870.
13. Chabinyc, M. L.; Brauman, J. I. J. Phys. Chem. A 1999,103,9163-9166.
14. Squires, R. R.; Bierbaum, V. M.; Grabowski, J. J.; DePuy, C. H. J. Am. Chem. Soc. 1983, 105, 5185-5192.
15. Grabowski, J. J.; DePuy, C. H.; Bierbaum, V. M. J. Am. Chem. Soc. 1983,105, 2565-2571.
16. Vogel, A. I. Practical Organic Chemistry; John Wiley & Sons Inc.: New York, 1956.
17. Hanst, P. L.; Calvert, J. G. J. Phys. Chem. 1959, 63, 104-110.
18. Stevens, W.; vanEs, A. Red. Trav. Chim. Pays-Bos 1964,83, 1287-1295.
19. Caldwell, G.; Bartmess, J. Org. Mass. Spectrom. 1982,17, 19-20.
20. Zhong, M.; Brauman, J. I. J. Am. Chem. Soc. 1996,118, 636-641.
21. Blair, L. K.; Isolani, P. C.; Riveros, J. M. J. Am. Chem. Soc. 1973, 95, 1057-1060.
22. DePuy, C.; Grabowski, J. J.; Bierbaum, V. M.; Ingemann, S.; Nibbering, N. M. M. J. Am. Chem. Soc. 1985, 707, 1093-1098.
23. Meot-Ner, M.; Sieck, L. W. J. Am. Chem. Soc. 1986,108, 7525-7529.
24. Paul, G. J. C; Kebarle, P. J. Phys. Chem. 1990, 94, 5184-5189.
25. Previous work demonstrated that deprotonation of the acetylenic hydrogen is both kinetically and thermodynamically more favorable than the benzylic hydrogens. Therefore, the anion in the p-tolylacetylene complexes was assumed to be the acetylide isomer. Also, the complexation energy of benzyl isomer is expected to be much lower, because the structurally similar benzyl-methanol complexes have been calculated to be weakly bound ∼12 kcal/mol. Chabinyc, M. L., Brauman, J. I. J. Am. Chem. Soc. 2000, 722, 3371-3378.
26. Barlow, S. E; Dang, T. T.; Bierbaum, V. M. J. Am. Chem. Soc. 1990,112, 6832-6838.
27. East, A. L. L.; Radom, L. J. Chem. Phys. 1997, 700, 6655-6674.
28. Benson, S. W. Thermochemlcal Kinetics; 2nd ed.; Wiley: New York, 1976.
29. Meot-Ner, M.; Sieck, L. W. J. Phys. Chem. 1986, 90, 6687-6690.
30. Bartmess, J. E. In NIST Chemistry WebBook, NIST Standard Reference Database 69; Mallard, W. G., Linstrom, P. J., Eds.; National Institute of Standards and Technology: Gaithersburg, MD, 1998.
31. Ervin, K. M.; et al. J. Am. Chem. Soc. 1990,112, 5750-5759.
32. Chabinyc, M. L.; Brauman, J. I. J. Am. Chem. Soc. 2000, 722,3371-3378.
33. Chabinyc, M. L.; Craig, S. L.; Regan, C. K.; Brauman, J. I. Science 1998,279,1882-1886.
34. Su, T.; Chesnavich, W. J. J. Chem. Phys. 1982, 76, 5183-5185.
35. Gilbert, R. G.; Smith, S. C. Theory of Unimolecular and Recombination Reactions; Blackwell Scientific: Oxford, 1990.
36. Wladkowski, B. D.; Lim, K. F.; Allen, W. D.; Brauman, J. I. J. Am. Chem. Soc. 1992, 114, 9136-9153.
37. Frisch, M. J.; et al. Gaussian94 Rev C.3; Gaussian, Inc.: Pittsburgh, PA, 1995.
38. Scott, A. P.; Radom, L. J. Phys. Chem. 1996,100, 16502-16513.
39. Pimentel, G. C.; McClellan, A. L. The Hydrogen Bond; Freeman: San Francisco, 1960.
40. Ions and Ion Pairs in Organic Reactions; Szwarc, M., Ed.; Wiley-Interscience: New York, 1972.
41. Bell, R. P. The Proton in Chemistry; Cornell University Press: Ithaca, NY, 1973.
42. Jencks, W. P. Catalysis in Chemistry and Enzymology; Dover Publications: New York, 1987.
43. Positive ion complexes have been widely examined as well. For recent work, see: Meot-Ner, M.; Sieck, L. W.; Koretke, K. K.; Deakyne, C. A. J. Am. Chem. Soc. 1997, 119, 10430-10438.
44. Larson, J. W.; McMahon, T. B. J. Am. Chem. Soc. 1987, 709 (9), 6230-6236.
45. Ayotte, P.; Bailey, C. G.; Johnson, M. A. J. Phys. Chem. A 1998, 702, 3067-3071.
46. Gatev, G. G.; Zhong, M.; Brauman, J. I. J. Phys. Org. Chem. 1997, 70, 531-536.
47. Bradforth, S. E.; Arnold, D. W.; Metz, R. B.; Weaver, A.; Neumark, D. M. y. Phys. Chem. 1991, 95, 8066-8078.
48. (a) Peiris, D. M.; Riveras, J. M.; Eyler, J. R. Int. J. Mass. Spectrom. Ion Proc. 1996, 759, 169-183.
49. (b) Weiser, P. S.; Wild, D. A.; Bieske, E. J. Chem. Phys. Lett. 1999, 299, 303-308.
50. Weiser, P. S.; Wild, D. A.; Bieske, E. J. J. Chem. Phys. 1999,110, 9443-9449.
51. We have been unable to synthesize the benzyl-methanol complex under our conditions, suggesting it is weakly bound. Ab initio calculations suggest the complex is only bound by ∼12 kcal/mol. Gatev, G. G.; Zhong, M.; Brauman, J. I. J. Phys. Org. Chem. 1997, 70, 531-536
52. Larson, J. W.; McMahon, T. B. J. Am. Chem. Soc. 1987, 770, 1087-1093.
53. Ellenberger, M. R.; Farneth, W. E.; Dixon, D. A. J. Phys. Chem. 1981, 85, 4-7.
54. Wilkinson, F. E.; Peschke, M.; Szulejko, J. E.; McMahon, T. B. Int. J. Mass. Spectrom. Ion Proc. 1998, 775, 225-240.
55. Mihalick, J. E.; Gatev, G. G.; Brauman, J. I. J. Am. Chem. Soc. 1996, 77S, 12424-12431.
56. Wladkowski, B. D.; East, A. L. L.; Mihalick, J. E.; Allen, W. D.; Brauman, J. I. J. Chem. Phys. 1993, 700, 2058-2088.
57. These relationships are also observed in the condensed phase. For recent work, see: Shan, S.-O.; Loh, S.; Herschlag, D. Science 1996, 272, 97-101.
58. Larson, J. W.; McMahon, T. B. J. Am. Chem. Soc. 1983,705,2944-2950.
59. Proton transfer could occur between the acetylene and the acetylide in the collision complex, followed by simple solvent switching. We are unable to determine if this pathway is operative because there is no change in mass of the resulting complex.
60. complex = -15.5 kcal/mol (ref 8).
61. Estimates are based on the pressure range obtainable and typical signal-to-noise ratios.
62. 3 complexes. Calculations at the MP2/aug-cc-p-VDZ//HF/aug-cc-p-VDZ level gave similar results, ruling out the possibility of a basis-set-dependent error. One possibility is basis set superposition error, but this error would tend to make the complexation energies less exothermic.
63. - + phenylacetylene reaction. We observed a similar result with the proton-transfer reaction of methoxide with these acetylenes. It is unclear whether the origin is a true thermodynamic barrier or dynamic effects during the reaction. Chabinyc, M. L.; Brauman, J. I. ref 31.
64. Huskey, W. P. J. Am. Chem. Soc. 1996, 118, 1663-1668.
65. Kreevoy, M. M.; Liang, T. M. J. Am. Chem. Soc. 1980,102,3315-3322.
66. Fraser, G. T.; Lovas, F. J.; Suenram, R. D.; Nelson, D. D. N., Jr.; Kleraperer, W. J. Chem. Phys. 1986, 84, 5983-5988.
67. Clearly, charge distributions are perturbed in these strongly bound complexes and charge-transfer effects may be important. However, our data suggest that the charge-dipole component to the interaction is the dominant factor. See also: Weinhold, F. THEOCHEM 1997, 398-399, 181-197.
68. Fraser, G. T.; Leopold, K. R.; Klemperer, W. J.'Chem. Phys. 1984, 80, 1423-1426.
69. Cybulski, S. M.; Scheiner, S. J. Am. Chem. Soc. 1987,109,4199-4206.
70. Wiberg, K. B.; Rablen, P. R. J. Am. Chem. Soc. 1993,115, 9234-9242.
71. Gerlt, J. A.; Kreevoy, M. M.; Cleland, W. W.; Frey, P. A. Chem. Biol 1997, 4, 259-267.
72. Magnoli, D. E.; Murdoch, J. R. J. Am. Chem. Soc. 1981,103,7465-7469.
73. Scheiner, S.; Redfern, P. J. Phys. Chem. 1986, 90, 2969-2974.
74. (71 ) It is difficult to uncover the origin of substituent effects for acetylides because there is no unambiguous theoretical method to separate π and σ orbital effects. See: Schleyer, P. v. R. Pure Appl. Chem. 1987, 59, 1647-1660.
75. de Beer, E.; Kim, E. H.; Neumark, D. M.; Gunion, R. F.; Linebcrger, W. C. J. Chem. Phys. 1995, 99, 13627-13636.