Direct observation of the wheland intermediate in electrophilic aromatic substitution. Reversible formation of nitrosoarenium cations

Journal of the American Chemical Society

Volumn 122, Issue 34, 2000, Pages 8279-8288

  Hubig, Stephan M ^a   Kochi, Jay K ^a  

^a University of Houston ^*  (United States)

Author keywords

[No Author keywords available]

Indexed keywords

CATION; NAPHTHALENE DERIVATIVE; NITRIC OXIDE; NITROSO DERIVATIVE; POLYCYCLIC AROMATIC HYDROCARBON DERIVATIVE;

ABSORPTION SPECTROSCOPY; ARTICLE; CHEMICAL REACTION KINETICS; COMPLEX FORMATION; ELECTRON TRANSPORT; NITROSATION; TEMPERATURE DEPENDENCE;

EID: 0034734326     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja001318u     Document Type: Article

References (74)

1. (a) Lowery, T. H.; Richardson, K. S. Mechanism and Theory in Organic Chemistry, 3rd ed.; Harper and Row Publishers: New York, 1987; p 623.
2. (b) March, J. Advanced Organic Chemistry; John Wiley & Sons: New York, 1992; p 501.
3. Rathore, R.; Kochi, J. K. Adv. Phys. Org. Chem. 2000, 35, 193.
4. See, for example: (a) McMullan, R. K.; Koetzle, T. F.; Fritchie, C. J. Acta Crystallogr. 1997, B53, 645. (b) Mascal, M.; Hansen, J.; Blake, A. J.; Li, W.-S. Chem. Commun. 1998, 355. (c) Baysanov, A. S.; Crabtree, S. P.; Howard, J. A. K.; Lehmann, C. W.; Kilner, M. J. Organomet. Chem. 1998, 550, 59. (d) See also refs 2 and 15.
5. See, for example: (a) McMullan, R. K.; Koetzle, T. F.; Fritchie, C. J. Acta Crystallogr. 1997, B53, 645. (b) Mascal, M.; Hansen, J.; Blake, A. J.; Li, W.-S. Chem. Commun. 1998, 355. (c) Baysanov, A. S.; Crabtree, S. P.; Howard, J. A. K.; Lehmann, C. W.; Kilner, M. J. Organomet. Chem. 1998, 550, 59. (d) See also refs 2 and 15.
6. See, for example: (a) McMullan, R. K.; Koetzle, T. F.; Fritchie, C. J. Acta Crystallogr. 1997, B53, 645. (b) Mascal, M.; Hansen, J.; Blake, A. J.; Li, W.-S. Chem. Commun. 1998, 355. (c) Baysanov, A. S.; Crabtree, S. P.; Howard, J. A. K.; Lehmann, C. W.; Kilner, M. J. Organomet. Chem. 1998, 550, 59. (d) See also refs 2 and 15.
7. See, for example: (a) McMullan, R. K.; Koetzle, T. F.; Fritchie, C. J. Acta Crystallogr. 1997, B53, 645. (b) Mascal, M.; Hansen, J.; Blake, A. J.; Li, W.-S. Chem. Commun. 1998, 355. (c) Baysanov, A. S.; Crabtree, S. P.; Howard, J. A. K.; Lehmann, C. W.; Kilner, M. J. Organomet. Chem. 1998, 550, 59. (d) See also refs 2 and 15.
8. 4f,g etc. have been characterized by NMR spectroscopy and/or X-ray crystallography.
9. (b) Rathore, R.; Hecht, J.; Kochi, J. K. J. Am. Chem. Soc. 1998, 120, 13278.
10. (c) Olah, G. A.; Lin, H. C.; Mo, Y. K. J. Am. Chem. Soc. 1972, 94, 3667.
11. (d) Mamatyuk, V. I.; Rezvukhin, A. I.; Detsina, A. N.; Buraev, V. I.; Isaev, I. S.; Koptyug, V. A. Zh. Org. Khim. 1973, 9, 2429.
12. (e) See also: Koptyug, V. A. Top. Curr. Chem. 1984, 122, 1.
13. (f) Borodkin, G. I.; Nagi, S. M.; Gatilov, Y. V.; Shakirov, M. M.; Rybalvo, T. V.; Shubin, V. G. Zh. Org. Khim. 1992, 28, 1806.
14. (g) Doering, W. von E.; Saunders, M.; Boyton, H. G.; Earhart, H. W.; Wadley, E. F.; Edwards, W. R.; Laber, G. Tetrahedron 1958, 4, 178.
15. (h) Recently, protonated hexamethylbenzene, pentamethylbenzene, and mesitylene have been isolated as crystalline salts, and the structure of protonated pentamethylbenzenium has been determined by X-ray crystallography. See: Reed, C. A.; Fackler, N. L. P.; Kim, K.-C.; Stasko, D.; Evans, D. R.; Boyd, P. D. W.; Rickard, C. E. F. J. Am. Chem. Soc. 1999, 121, 6314.
16. 5d etc.
17. (b) Bockman, T. M.; Kochi, J. K. J. Phys. Org. Chem. 1994, 7, 325 and references therein.
18. (c) Wallis, J. M.; Kochi, J. K. J. Am. Chem. Soc. 1988, 110, 8207.
19. (d) Hubig, S. M.; Kochi, J. K. In Electron Transfer in Chemistry; Balzani, V., Ed.; Wiley-VCH: New York, in press.
20. Olah, G. A.; Malhotra, R.; Narang, S. C. Nitration: Methods and Mechanisms; VCH: New York, 1989.
21. The lack of deuterium isotope effects in the kinetics of nitrations confirms the fast deprotonation rates. See ref 6.
22. See also Koptyug et al. in refs 4d and 4e.
23. Williams, D. L. H. Nitrosation; Cambridge University Press: Cambridge, 1988.
24. Challis, B. C.; Higgins, R. J.; Lawson, A. J. J. Chem. Soc., Perkin Trans. 2 1972, 1831.
25. 9 However, under acidic, NO-saturated, nonaqueous conditions, nitrosations of toluene and xylene can be achieved in moderate yields. See: Atherton, J. H.; Moodie, R. B.; Noble, D. R. J. Chem. Soc., Perkin Trans. 2 1999, 699.
26. Challis, B. C.; Higgins, R. J. J. Chem. Soc., Perkin Trans. 2 1973, 1597.
27. Dix, L. R.; Moodie, R. B. J. Chem. Soc., Perkin Trans. 2 1968, 1097.
28. Bosch, E.; Kochi, J. K. J. Org. Chem. 1994, 59, 5573. For a rationalization of the deuterium kinetic isotope effect, see: Lindeman, S. V.; Bosch, E.; Kochi, J. K. J. Chem. Soc., Perkin Trans. 2, in press.
29. Bosch, E.; Kochi, J. K. J. Org. Chem. 1994, 59, 5573. For a rationalization of the deuterium kinetic isotope effect, see: Lindeman, S. V.; Bosch, E.; Kochi, J. K. J. Chem. Soc., Perkin Trans. 2, in press.
30. Kim, E. K.; Kochi, J. K. J. Am. Chem. Soc. 1991, 113, 4962.
31. Reents, W. D.; Freiser, B. S. J. Am. Chem. Soc. 1980, 102, 271.
32. Kim, E. K.; Kochi, J. K. J. Org. Chem. 1989, 54, 1692.
33. Eberson, L.; Radner, F. Acta Chem. Scand 1984, B38, 861.
34. Lee, K. Y.; Kochi, J. K. J. Chem. Soc., Perkin Trans. 2 1994, 237.
35. • occurs at nearly diffusion-controlled rates which are independent of the donor strength of the aromatic substrate. See: Kim, E. K.; Bockman, T. M.; Kochi, J. K. J. Am. Chem. Soc. 1993, 115, 3091.
36. Bockman, T. M.; Karpinski, Z. J.; Sankararaman, S.; Kochi, J. K. J. Am. Chem. Soc. 1992, 114, 1970.
37. 23 (23) (a) Wynne, K.; Galli, C.; Hochstrasser, R. M. J. Chem. Phys. 1994, 100, 4797. (b) Asahi, T.; Mataga, N. J. Phys. Chem. 1989, 93, 6575. (c) Hubig, S. M.; Bockman, T. M.; Kochi, J. K. J. Am. Chem. Soc. 1996, 118, 3842.
38. 23 (23) (a) Wynne, K.; Galli, C.; Hochstrasser, R. M. J. Chem. Phys. 1994, 100, 4797. (b) Asahi, T.; Mataga, N. J. Phys. Chem. 1989, 93, 6575. (c) Hubig, S. M.; Bockman, T. M.; Kochi, J. K. J. Am. Chem. Soc. 1996, 118, 3842.
39. 23 (23) (a) Wynne, K.; Galli, C.; Hochstrasser, R. M. J. Chem. Phys. 1994, 100, 4797. (b) Asahi, T.; Mataga, N. J. Phys. Chem. 1989, 93, 6575. (c) Hubig, S. M.; Bockman, T. M.; Kochi, J. K. J. Am. Chem. Soc. 1996, 118, 3842.
40. Sehested, K.; Holcman, J.; Hart, E. J. J. Phys. Chem. 1977, 81, 1363.
41. The preliminary assignment will be substantiated throughout this report by a thorough analysis of its spectroscopic and kinetic properties.
42. For the absorption spectra of polyalkylbenzene cation radicals, see refs 21, 24, and 32 and references therein.
43. -1. See: Moore, J. W.; Pearson, R. G. Kinetics and Mechanism, 2nd ed.; Wiley: New York, 1981; p 239f.
44. The hexaphenylbenzene cation radical was also generated by electron-transfer quenching of photoexcited chloranil. Compare: Rathore, R.; Hubig, S. M.; Kochi, J. K. J. Am. Chem. Soc. 1997, 119, 11468.
45. -1 at 195 K. Extrapolation to [HMB] = 0 led to a lifetime of τ = 20 μs at 195 K.
46. -1 at T = 195 K, which is 30 times slower than that of HMB.
47. + EDA π-complex which is stable at low (-78 °C) temperatures.
48. Shida, T. Electronic Absorption Spectra of Radical Ions; Elsevier: Amsterdam, 1988; p 19.
49. (a) Kilpatrick, M.; Hyman, W. H. J. Am. Chem. Soc. 1958, 80, 77.
50. (b) Deno, N. C.; Groves, P. T.; Saines, G. J. Am. Chem. Soc. 1959, 81, 5790.
51. (a) See Rathore et al. in ref 4b.
52. (b) See ref 4e, p 97.
53. Dhanasekaran, T.; Kochi, J. K., unpublished results.
54. 13C NMR) and X-ray structures of various hexaalkylbenzenium ions, see: Hubig, S. M.; Kochi, J. K. J. Org. Chem., in press.
55. 4f,37b
56. (b) Dhanasekaran, T.; Lindeman, S. V.; Kochi, J. K., unpublished results.
57. CL) of nitrosoarenium from the radical pair.
58. Back-electron transfer in ion-radical pairs follows first-order kinetics since no diffusional processes are involved.
59. 38 we cannot discount a direct (one-step) alternative suggested by a reviewer involving the heterolytic cleavage of the NO-arene bond.
60. Rathore, R.; Lindeman, S. V.; Kochi, J. K. J. Am. Chem Soc. 1997, 119, 9393.
61. ET does not include any inner-sphere component to electron-transfer.
62. ET does not include any inner-sphere component to electron-transfer.
63. -1 approach those of barrier-free reactions. See ref 27, p 173.
64. 14,15
65. 41
66. 14
67. + EDA complexes. However, mere are conflicting results about the Wheland intermediate, viz., nitrosoarenium, which -depending on the method and level of the calculation - is obtained either as a more or less stable minimum or as a saddle point (transition state) between the EDA complex and N-protonated nitrosobenzene. Our experimental results reported here support the CISD/6-31G(d) calculations which predict a large energy barrier for the conversion of the σ-complex to an N-protonated nitrosobenzene and thus identify the deprotonation of the Wheland intermediate as the rate-determining step,
68. (c) Shokov, S.; Wheeler, R. A. J. Phys. Chem. 1999, 103, 3A, 4261.
69. Rathore, R., unpublished results.
70. Rathore, R.; Bosch, E.; Kochi, J. K. Tetrahedron 1994, 50, 6727.
71. Rathore, R.; Kochi, J. K. J. Org. Chem. 1995, 60, 4399.
72. Rathore, R.; Kochi, J. K. Acta Chem. Scand 1998, 52, 114.
73. Perrin, D. D.; Armarego, W. L. F.; Perrin, D. R. Purification of Laboratory Chemicals, 2nd ed; Pergamon: New York, 1980.
74. Bockman, T. M.; Kochi, J. K. J. Chem. Soc., Perkin Trans. 2 1996, 1633.