Barrierless electron transfer bond fragmentation reactions

Journal of the American Chemical Society

Volumn 126, Issue 43, 2004, Pages 14071-14078

  Lorance, Edward D ^a   Kramer, Wolfgang H ^a   Gould, Ian R ^a  

^a ARIZONA STATE UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

CHEMICAL BONDS; FREE RADICALS; MOLECULAR STRUCTURE; POTENTIAL ENERGY;

BOND FRAGMENTATION; ELECTRON TRANSFER BOND; VIBRATIONAL PERIODS;

ELECTRON TRANSITIONS;

RADICAL;

ARTICLE; CHEMICAL BOND; CHEMICAL REACTION; CHEMICAL STRUCTURE; ELECTRIC POTENTIAL; ELECTRON TRANSPORT; ELECTRONICS; MOLECULAR MODEL; REACTION ANALYSIS; VIBRATION;

EID: 7444269052     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja030438+     Document Type: Article

References (104)

1. See, for example: (a) Maslak, P. Top. Curr. Chem. 1993, 168, 1. (b) Saveant, J.-M. Acc. Chem. Res. 1993, 26, 455. (c) Albini, A.; Fasani, E.; d'Alessandro, N. Coord. Chem. Rev. 1993, 125, 269. (d) Saveant, J.-M. Adv. Electron-Transfer Chem. 1994, 4, 53. (e) Gaillard, E. R.; Whitten, D. G. Acc. Chem. Res. 1996, 29, 292.
2. See, for example: (a) Maslak, P. Top. Curr. Chem. 1993, 168, 1. (b) Saveant, J.-M. Acc. Chem. Res. 1993, 26, 455. (c) Albini, A.; Fasani, E.; d'Alessandro, N. Coord. Chem. Rev. 1993, 125, 269. (d) Saveant, J.-M. Adv. Electron-Transfer Chem. 1994, 4, 53. (e) Gaillard, E. R.; Whitten, D. G. Acc. Chem. Res. 1996, 29, 292.
3. See, for example: (a) Maslak, P. Top. Curr. Chem. 1993, 168, 1. (b) Saveant, J.-M. Acc. Chem. Res. 1993, 26, 455. (c) Albini, A.; Fasani, E.; d'Alessandro, N. Coord. Chem. Rev. 1993, 125, 269. (d) Saveant, J.-M. Adv. Electron-Transfer Chem. 1994, 4, 53. (e) Gaillard, E. R.; Whitten, D. G. Acc. Chem. Res. 1996, 29, 292.
4. See, for example: (a) Maslak, P. Top. Curr. Chem. 1993, 168, 1. (b) Saveant, J.-M. Acc. Chem. Res. 1993, 26, 455. (c) Albini, A.; Fasani, E.; d'Alessandro, N. Coord. Chem. Rev. 1993, 125, 269. (d) Saveant, J.-M. Adv. Electron-Transfer Chem. 1994, 4, 53. (e) Gaillard, E. R.; Whitten, D. G. Acc. Chem. Res. 1996, 29, 292.
5. See, for example: (a) Maslak, P. Top. Curr. Chem. 1993, 168, 1. (b) Saveant, J.-M. Acc. Chem. Res. 1993, 26, 455. (c) Albini, A.; Fasani, E.; d'Alessandro, N. Coord. Chem. Rev. 1993, 125, 269. (d) Saveant, J.-M. Adv. Electron-Transfer Chem. 1994, 4, 53. (e) Gaillard, E. R.; Whitten, D. G. Acc. Chem. Res. 1996, 29, 292.
6. (a) Crivello, J. V. Adv. Polym. Sci. 1984, 62, 1.
7. (b) Reiser, A. Photoreactive Polymers, the Science and Technology of Resists; Wiley: New York, 1989.
8. (c) Saeva, F. D Top. Curr. Chem. 1990, 156, 59.
9. (d) DeVoe, R. J.; Olofson, P. M.; Sahyun, M. R. V. Adv. Photochem. 1992, 17, 313.
10. (e) Saeva, F. D. Adv. Electron-Transfer Chem. 1994, 4, 1.
11. (f) Paczkowski, J.; Neckers, D. C. In Electron Transfer in Chemistry; Balzani, V., Ed.; Wiley-VCH: New York, 2001; Vol. 5, p 516.
12. (g) Gould, I. R.; Shukla, D.; Giesen, D.; Farid, S. Helv. Chim. Acta 2001, 84, 2796.
13. (a) Parker, V. D. Acta Chem. Scand. B 1981, B35, 595.
14. (b) Hammerich, O.; Parker, V. D. Acta Chem. Scand. B 1981, B37, 851.
15. (c) Koppang, M. D.; Woolsey, N. F.; Bartak, D. E. J. Am. Chem. Soc. 1985, 107, 4692.
16. (d) Maslak, P.; Guthrie, R. D. J. Am. Chem. Soc. 1986, 108, 2628.
17. (e) Maslak, P.; Narvaez, J. N. Angew. Chem. 1990, 4, 302.
18. (f) Ruhl, J. C.; Evans, D. H.; Hapiot, P.; Neta, P. J. Am. Chem. Soc. 1991, 113, 5188.
19. (g) Wu, F.; Guarr, T. F.; Guthrie, R. D. J. Phys. Org. Chem. 1992, 5, 7.
20. (h) Saveant, J. M. J. Phys. Chem. 1994, 98, 3716.
21. (i) Guthrie, R. D.; Patwardhan, M.; Chateauneuf, J. E. J. Phys. Org. Chem. 1994, 7, 147.
22. (j) Mathivanan, N.; Johnston, L. J.; Wayner, D. D. M. J. Phys. Chem. 1995, 99, 8190.
23. (k) Maslak, P.; Theroff, J. J. Am. Chem. Soc. 1996, 118, 7235.
24. (l) Andrieux, C. P.; Saveant, J.-M.; Tallec, A.; Tardivel, R.; Tardy, C. J. Am. Chem. Soc. 1996, 118, 9788.
25. (m) Andrieux, C. P.; Combellas, C.; Kanoufi, F.; Saveant, J.-M.; Thiebault, A. J. Am. Chem. Soc. 1997, 119, 9527.
26. (n) Benassi, R.; Bertarini, C.; Taddei, F. J. Chem. Soc., Perkin Trans. 2 1997, 2263.
27. (o) Borsari, M.; Fontanesi, C.; Gavioli, G. Curr. Top. Electrochem. 1997, 5 167.
28. (p) Zheng, Z.-R.; Evans, D. H.; Chan-Shing, E. S.; Lessard, J. J. Am. Chem. Soc. 1999, 121, 9429.
29. (q) Eberson, L. Acta Chem. Scand. 1999, 53, 751.
30. (r) Beregovaya, I. V.; Shchegoleva, L. N. Chem. Phys. Lett. 2001, 348, 501.
31. (s) Andrieux, C. P.; Farriol, M.; Gallardo, I.; Marquet, J. J. Chem. Soc., Perkin Trans. 2 2002, 985.
32. (t) Costentin, C.; Robert, M.; Saveant, J.-M. J. Am. Chem. Soc. 2003, 125, 105.
33. See, for example: (a) Andrieux, C. P.; Le Gorande, A.; Saveant, J.-M. J. Am. Chem. Soc. 1992, 114, 6892. (b) Grimshaw, J.; Langan, J. R.; Salmon, G. A. J. Chem. Soc., Faraday Trans 1994, 90, 75. (c) Andrieux, C. P.; Robert, M.; Saeva. F. D.; Saveant, J.-M. J. Am. Chem. Soc. 1994, 116, 7864. (d) Saveant, J.-M. Adv. Electron-Transfer Chem. 1994, 4, 53. (e) Adcock, W.; Andrieux, C. P.; Clark, C. I.; Neudeck, A.; Saveant, J.-M.; Tardy, C. J. Am. Chem. Soc. 1995, 117, 8285. (f) Andrieux, C. P.; Saveant, J.-M.; Tallec, A.; Tardivel, R.; Tardy, C. J. Am. Chem. Soc. 1997, 119, 2420. (g) Andrieux, C. P.; Saveant, J.-M.; Tardy, C. J. Am. Chem. Soc. 1997, 119, 11546. (h) Zhong, D.; Zewail, A. H. Proc. Natl. Acad Sci. U.S.A. 1999, 96, 2602. (i) Costentin, C.; Hapiot, P.; Medebielle, M.; Saveant, J.-M. J. Am. Chem. Soc. 2000, 122, 5623. (j) Pause, L.; Robert, M.; Saveant, J.-M. J. Am. Chem. Soc. 2000, 122, 9829. (k) Soriano, A.; Silla, E.; Tunon, I. J. Chem. Phys. 2002, 116, 6102. (l) Antonello, S.; Crisma, M.; Formaggio, F.; Moretto, A.; Taddei, F.; Toniolo, C.; Maran, F. J. Am. Chem. Soc. 2002, 124, 11503. (m) Cardinale, A.; Isse, A. A.; Gennaro, A.; Robert, M.; Saveant, J.-M. J. Am. Chem. Soc. 2002, 124, 13533.
34. See, for example: (a) Andrieux, C. P.; Le Gorande, A.; Saveant, J.-M. J. Am. Chem. Soc. 1992, 114, 6892. (b) Grimshaw, J.; Langan, J. R.; Salmon, G. A. J. Chem. Soc., Faraday Trans 1994, 90, 75. (c) Andrieux, C. P.; Robert, M.; Saeva. F. D.; Saveant, J.-M. J. Am. Chem. Soc. 1994, 116, 7864. (d) Saveant, J.-M. Adv. Electron-Transfer Chem. 1994, 4, 53. (e) Adcock, W.; Andrieux, C. P.; Clark, C. I.; Neudeck, A.; Saveant, J.-M.; Tardy, C. J. Am. Chem. Soc. 1995, 117, 8285. (f) Andrieux, C. P.; Saveant, J.-M.; Tallec, A.; Tardivel, R.; Tardy, C. J. Am. Chem. Soc. 1997, 119, 2420. (g) Andrieux, C. P.; Saveant, J.-M.; Tardy, C. J. Am. Chem. Soc. 1997, 119, 11546. (h) Zhong, D.; Zewail, A. H. Proc. Natl. Acad Sci. U.S.A. 1999, 96, 2602. (i) Costentin, C.; Hapiot, P.; Medebielle, M.; Saveant, J.-M. J. Am. Chem. Soc. 2000, 122, 5623. (j) Pause, L.; Robert, M.; Saveant, J.-M. J. Am. Chem. Soc. 2000, 122, 9829. (k) Soriano, A.; Silla, E.; Tunon, I. J. Chem. Phys. 2002, 116, 6102. (l) Antonello, S.; Crisma, M.; Formaggio, F.; Moretto, A.; Taddei, F.; Toniolo, C.; Maran, F. J. Am. Chem. Soc. 2002, 124, 11503. (m) Cardinale, A.; Isse, A. A.; Gennaro, A.; Robert, M.; Saveant, J.-M. J. Am. Chem. Soc. 2002, 124, 13533.
35. See, for example: (a) Andrieux, C. P.; Le Gorande, A.; Saveant, J.-M. J. Am. Chem. Soc. 1992, 114, 6892. (b) Grimshaw, J.; Langan, J. R.; Salmon, G. A. J. Chem. Soc., Faraday Trans 1994, 90, 75. (c) Andrieux, C. P.; Robert, M.; Saeva. F. D.; Saveant, J.-M. J. Am. Chem. Soc. 1994, 116, 7864. (d) Saveant, J.-M. Adv. Electron-Transfer Chem. 1994, 4, 53. (e) Adcock, W.; Andrieux, C. P.; Clark, C. I.; Neudeck, A.; Saveant, J.-M.; Tardy, C. J. Am. Chem. Soc. 1995, 117, 8285. (f) Andrieux, C. P.; Saveant, J.-M.; Tallec, A.; Tardivel, R.; Tardy, C. J. Am. Chem. Soc. 1997, 119, 2420. (g) Andrieux, C. P.; Saveant, J.-M.; Tardy, C. J. Am. Chem. Soc. 1997, 119, 11546. (h) Zhong, D.; Zewail, A. H. Proc. Natl. Acad Sci. U.S.A. 1999, 96, 2602. (i) Costentin, C.; Hapiot, P.; Medebielle, M.; Saveant, J.-M. J. Am. Chem. Soc. 2000, 122, 5623. (j) Pause, L.; Robert, M.; Saveant, J.-M. J. Am. Chem. Soc. 2000, 122, 9829. (k) Soriano, A.; Silla, E.; Tunon, I. J. Chem. Phys. 2002, 116, 6102. (l) Antonello, S.; Crisma, M.; Formaggio, F.; Moretto, A.; Taddei, F.; Toniolo, C.; Maran, F. J. Am. Chem. Soc. 2002, 124, 11503. (m) Cardinale, A.; Isse, A. A.; Gennaro, A.; Robert, M.; Saveant, J.-M. J. Am. Chem. Soc. 2002, 124, 13533.
36. See, for example: (a) Andrieux, C. P.; Le Gorande, A.; Saveant, J.-M. J. Am. Chem. Soc. 1992, 114, 6892. (b) Grimshaw, J.; Langan, J. R.; Salmon, G. A. J. Chem. Soc., Faraday Trans 1994, 90, 75. (c) Andrieux, C. P.; Robert, M.; Saeva. F. D.; Saveant, J.-M. J. Am. Chem. Soc. 1994, 116, 7864. (d) Saveant, J.-M. Adv. Electron-Transfer Chem. 1994, 4, 53. (e) Adcock, W.; Andrieux, C. P.; Clark, C. I.; Neudeck, A.; Saveant, J.-M.; Tardy, C. J. Am. Chem. Soc. 1995, 117, 8285. (f) Andrieux, C. P.; Saveant, J.-M.; Tallec, A.; Tardivel, R.; Tardy, C. J. Am. Chem. Soc. 1997, 119, 2420. (g) Andrieux, C. P.; Saveant, J.-M.; Tardy, C. J. Am. Chem. Soc. 1997, 119, 11546. (h) Zhong, D.; Zewail, A. H. Proc. Natl. Acad Sci. U.S.A. 1999, 96, 2602. (i) Costentin, C.; Hapiot, P.; Medebielle, M.; Saveant, J.-M. J. Am. Chem. Soc. 2000, 122, 5623. (j) Pause, L.; Robert, M.; Saveant, J.-M. J. Am. Chem. Soc. 2000, 122, 9829. (k) Soriano, A.; Silla, E.; Tunon, I. J. Chem. Phys. 2002, 116, 6102. (l) Antonello, S.; Crisma, M.; Formaggio, F.; Moretto, A.; Taddei, F.; Toniolo, C.; Maran, F. J. Am. Chem. Soc. 2002, 124, 11503. (m) Cardinale, A.; Isse, A. A.; Gennaro, A.; Robert, M.; Saveant, J.-M. J. Am. Chem. Soc. 2002, 124, 13533.
37. See, for example: (a) Andrieux, C. P.; Le Gorande, A.; Saveant, J.-M. J. Am. Chem. Soc. 1992, 114, 6892. (b) Grimshaw, J.; Langan, J. R.; Salmon, G. A. J. Chem. Soc., Faraday Trans 1994, 90, 75. (c) Andrieux, C. P.; Robert, M.; Saeva. F. D.; Saveant, J.-M. J. Am. Chem. Soc. 1994, 116, 7864. (d) Saveant, J.-M. Adv. Electron-Transfer Chem. 1994, 4, 53. (e) Adcock, W.; Andrieux, C. P.; Clark, C. I.; Neudeck, A.; Saveant, J.-M.; Tardy, C. J. Am. Chem. Soc. 1995, 117, 8285. (f) Andrieux, C. P.; Saveant, J.-M.; Tallec, A.; Tardivel, R.; Tardy, C. J. Am. Chem. Soc. 1997, 119, 2420. (g) Andrieux, C. P.; Saveant, J.-M.; Tardy, C. J. Am. Chem. Soc. 1997, 119, 11546. (h) Zhong, D.; Zewail, A. H. Proc. Natl. Acad Sci. U.S.A. 1999, 96, 2602. (i) Costentin, C.; Hapiot, P.; Medebielle, M.; Saveant, J.-M. J. Am. Chem. Soc. 2000, 122, 5623. (j) Pause, L.; Robert, M.; Saveant, J.-M. J. Am. Chem. Soc. 2000, 122, 9829. (k) Soriano, A.; Silla, E.; Tunon, I. J. Chem. Phys. 2002, 116, 6102. (l) Antonello, S.; Crisma, M.; Formaggio, F.; Moretto, A.; Taddei, F.; Toniolo, C.; Maran, F. J. Am. Chem. Soc. 2002, 124, 11503. (m) Cardinale, A.; Isse, A. A.; Gennaro, A.; Robert, M.; Saveant, J.-M. J. Am. Chem. Soc. 2002, 124, 13533.
38. See, for example: (a) Andrieux, C. P.; Le Gorande, A.; Saveant, J.-M. J. Am. Chem. Soc. 1992, 114, 6892. (b) Grimshaw, J.; Langan, J. R.; Salmon, G. A. J. Chem. Soc., Faraday Trans 1994, 90, 75. (c) Andrieux, C. P.; Robert, M.; Saeva. F. D.; Saveant, J.-M. J. Am. Chem. Soc. 1994, 116, 7864. (d) Saveant, J.-M. Adv. Electron-Transfer Chem. 1994, 4, 53. (e) Adcock, W.; Andrieux, C. P.; Clark, C. I.; Neudeck, A.; Saveant, J.-M.; Tardy, C. J. Am. Chem. Soc. 1995, 117, 8285. (f) Andrieux, C. P.; Saveant, J.-M.; Tallec, A.; Tardivel, R.; Tardy, C. J. Am. Chem. Soc. 1997, 119, 2420. (g) Andrieux, C. P.; Saveant, J.-M.; Tardy, C. J. Am. Chem. Soc. 1997, 119, 11546. (h) Zhong, D.; Zewail, A. H. Proc. Natl. Acad Sci. U.S.A. 1999, 96, 2602. (i) Costentin, C.; Hapiot, P.; Medebielle, M.; Saveant, J.-M. J. Am. Chem. Soc. 2000, 122, 5623. (j) Pause, L.; Robert, M.; Saveant, J.-M. J. Am. Chem. Soc. 2000, 122, 9829. (k) Soriano, A.; Silla, E.; Tunon, I. J. Chem. Phys. 2002, 116, 6102. (l) Antonello, S.; Crisma, M.; Formaggio, F.; Moretto, A.; Taddei, F.; Toniolo, C.; Maran, F. J. Am. Chem. Soc. 2002, 124, 11503. (m) Cardinale, A.; Isse, A. A.; Gennaro, A.; Robert, M.; Saveant, J.-M. J. Am. Chem. Soc. 2002, 124, 13533.
39. See, for example: (a) Andrieux, C. P.; Le Gorande, A.; Saveant, J.-M. J. Am. Chem. Soc. 1992, 114, 6892. (b) Grimshaw, J.; Langan, J. R.; Salmon, G. A. J. Chem. Soc., Faraday Trans 1994, 90, 75. (c) Andrieux, C. P.; Robert, M.; Saeva. F. D.; Saveant, J.-M. J. Am. Chem. Soc. 1994, 116, 7864. (d) Saveant, J.-M. Adv. Electron-Transfer Chem. 1994, 4, 53. (e) Adcock, W.; Andrieux, C. P.; Clark, C. I.; Neudeck, A.; Saveant, J.-M.; Tardy, C. J. Am. Chem. Soc. 1995, 117, 8285. (f) Andrieux, C. P.; Saveant, J.-M.; Tallec, A.; Tardivel, R.; Tardy, C. J. Am. Chem. Soc. 1997, 119, 2420. (g) Andrieux, C. P.; Saveant, J.-M.; Tardy, C. J. Am. Chem. Soc. 1997, 119, 11546. (h) Zhong, D.; Zewail, A. H. Proc. Natl. Acad Sci. U.S.A. 1999, 96, 2602. (i) Costentin, C.; Hapiot, P.; Medebielle, M.; Saveant, J.-M. J. Am. Chem. Soc. 2000, 122, 5623. (j) Pause, L.; Robert, M.; Saveant, J.-M. J. Am. Chem. Soc. 2000, 122, 9829. (k) Soriano, A.; Silla, E.; Tunon, I. J. Chem. Phys. 2002, 116, 6102. (l) Antonello, S.; Crisma, M.; Formaggio, F.; Moretto, A.; Taddei, F.; Toniolo, C.; Maran, F. J. Am. Chem. Soc. 2002, 124, 11503. (m) Cardinale, A.; Isse, A. A.; Gennaro, A.; Robert, M.; Saveant, J.-M. J. Am. Chem. Soc. 2002, 124, 13533.
40. See, for example: (a) Andrieux, C. P.; Le Gorande, A.; Saveant, J.-M. J. Am. Chem. Soc. 1992, 114, 6892. (b) Grimshaw, J.; Langan, J. R.; Salmon, G. A. J. Chem. Soc., Faraday Trans 1994, 90, 75. (c) Andrieux, C. P.; Robert, M.; Saeva. F. D.; Saveant, J.-M. J. Am. Chem. Soc. 1994, 116, 7864. (d) Saveant, J.-M. Adv. Electron-Transfer Chem. 1994, 4, 53. (e) Adcock, W.; Andrieux, C. P.; Clark, C. I.; Neudeck, A.; Saveant, J.-M.; Tardy, C. J. Am. Chem. Soc. 1995, 117, 8285. (f) Andrieux, C. P.; Saveant, J.-M.; Tallec, A.; Tardivel, R.; Tardy, C. J. Am. Chem. Soc. 1997, 119, 2420. (g) Andrieux, C. P.; Saveant, J.-M.; Tardy, C. J. Am. Chem. Soc. 1997, 119, 11546. (h) Zhong, D.; Zewail, A. H. Proc. Natl. Acad Sci. U.S.A. 1999, 96, 2602. (i) Costentin, C.; Hapiot, P.; Medebielle, M.; Saveant, J.-M. J. Am. Chem. Soc. 2000, 122, 5623. (j) Pause, L.; Robert, M.; Saveant, J.-M. J. Am. Chem. Soc. 2000, 122, 9829. (k) Soriano, A.; Silla, E.; Tunon, I. J. Chem. Phys. 2002, 116, 6102. (l) Antonello, S.; Crisma, M.; Formaggio, F.; Moretto, A.; Taddei, F.; Toniolo, C.; Maran, F. J. Am. Chem. Soc. 2002, 124, 11503. (m) Cardinale, A.; Isse, A. A.; Gennaro, A.; Robert, M.; Saveant, J.-M. J. Am. Chem. Soc. 2002, 124, 13533.
41. See, for example: (a) Andrieux, C. P.; Le Gorande, A.; Saveant, J.-M. J. Am. Chem. Soc. 1992, 114, 6892. (b) Grimshaw, J.; Langan, J. R.; Salmon, G. A. J. Chem. Soc., Faraday Trans 1994, 90, 75. (c) Andrieux, C. P.; Robert, M.; Saeva. F. D.; Saveant, J.-M. J. Am. Chem. Soc. 1994, 116, 7864. (d) Saveant, J.-M. Adv. Electron-Transfer Chem. 1994, 4, 53. (e) Adcock, W.; Andrieux, C. P.; Clark, C. I.; Neudeck, A.; Saveant, J.-M.; Tardy, C. J. Am. Chem. Soc. 1995, 117, 8285. (f) Andrieux, C. P.; Saveant, J.-M.; Tallec, A.; Tardivel, R.; Tardy, C. J. Am. Chem. Soc. 1997, 119, 2420. (g) Andrieux, C. P.; Saveant, J.-M.; Tardy, C. J. Am. Chem. Soc. 1997, 119, 11546. (h) Zhong, D.; Zewail, A. H. Proc. Natl. Acad Sci. U.S.A. 1999, 96, 2602. (i) Costentin, C.; Hapiot, P.; Medebielle, M.; Saveant, J.-M. J. Am. Chem. Soc. 2000, 122, 5623. (j) Pause, L.; Robert, M.; Saveant, J.-M. J. Am. Chem. Soc. 2000, 122, 9829. (k) Soriano, A.; Silla, E.; Tunon, I. J. Chem. Phys. 2002, 116, 6102. (l) Antonello, S.; Crisma, M.; Formaggio, F.; Moretto, A.; Taddei, F.; Toniolo, C.; Maran, F. J. Am. Chem. Soc. 2002, 124, 11503. (m) Cardinale, A.; Isse, A. A.; Gennaro, A.; Robert, M.; Saveant, J.-M. J. Am. Chem. Soc. 2002, 124, 13533.
42. See, for example: (a) Andrieux, C. P.; Le Gorande, A.; Saveant, J.-M. J. Am. Chem. Soc. 1992, 114, 6892. (b) Grimshaw, J.; Langan, J. R.; Salmon, G. A. J. Chem. Soc., Faraday Trans 1994, 90, 75. (c) Andrieux, C. P.; Robert, M.; Saeva. F. D.; Saveant, J.-M. J. Am. Chem. Soc. 1994, 116, 7864. (d) Saveant, J.-M. Adv. Electron-Transfer Chem. 1994, 4, 53. (e) Adcock, W.; Andrieux, C. P.; Clark, C. I.; Neudeck, A.; Saveant, J.-M.; Tardy, C. J. Am. Chem. Soc. 1995, 117, 8285. (f) Andrieux, C. P.; Saveant, J.-M.; Tallec, A.; Tardivel, R.; Tardy, C. J. Am. Chem. Soc. 1997, 119, 2420. (g) Andrieux, C. P.; Saveant, J.-M.; Tardy, C. J. Am. Chem. Soc. 1997, 119, 11546. (h) Zhong, D.; Zewail, A. H. Proc. Natl. Acad Sci. U.S.A. 1999, 96, 2602. (i) Costentin, C.; Hapiot, P.; Medebielle, M.; Saveant, J.-M. J. Am. Chem. Soc. 2000, 122, 5623. (j) Pause, L.; Robert, M.; Saveant, J.-M. J. Am. Chem. Soc. 2000, 122, 9829. (k) Soriano, A.; Silla, E.; Tunon, I. J. Chem. Phys. 2002, 116, 6102. (l) Antonello, S.; Crisma, M.; Formaggio, F.; Moretto, A.; Taddei, F.; Toniolo, C.; Maran, F. J. Am. Chem. Soc. 2002, 124, 11503. (m) Cardinale, A.; Isse, A. A.; Gennaro, A.; Robert, M.; Saveant, J.-M. J. Am. Chem. Soc. 2002, 124, 13533.
43. See, for example: (a) Andrieux, C. P.; Le Gorande, A.; Saveant, J.-M. J. Am. Chem. Soc. 1992, 114, 6892. (b) Grimshaw, J.; Langan, J. R.; Salmon, G. A. J. Chem. Soc., Faraday Trans 1994, 90, 75. (c) Andrieux, C. P.; Robert, M.; Saeva. F. D.; Saveant, J.-M. J. Am. Chem. Soc. 1994, 116, 7864. (d) Saveant, J.-M. Adv. Electron-Transfer Chem. 1994, 4, 53. (e) Adcock, W.; Andrieux, C. P.; Clark, C. I.; Neudeck, A.; Saveant, J.-M.; Tardy, C. J. Am. Chem. Soc. 1995, 117, 8285. (f) Andrieux, C. P.; Saveant, J.-M.; Tallec, A.; Tardivel, R.; Tardy, C. J. Am. Chem. Soc. 1997, 119, 2420. (g) Andrieux, C. P.; Saveant, J.-M.; Tardy, C. J. Am. Chem. Soc. 1997, 119, 11546. (h) Zhong, D.; Zewail, A. H. Proc. Natl. Acad Sci. U.S.A. 1999, 96, 2602. (i) Costentin, C.; Hapiot, P.; Medebielle, M.; Saveant, J.-M. J. Am. Chem. Soc. 2000, 122, 5623. (j) Pause, L.; Robert, M.; Saveant, J.-M. J. Am. Chem. Soc. 2000, 122, 9829. (k) Soriano, A.; Silla, E.; Tunon, I. J. Chem. Phys. 2002, 116, 6102. (l) Antonello, S.; Crisma, M.; Formaggio, F.; Moretto, A.; Taddei, F.; Toniolo, C.; Maran, F. J. Am. Chem. Soc. 2002, 124, 11503. (m) Cardinale, A.; Isse, A. A.; Gennaro, A.; Robert, M.; Saveant, J.-M. J. Am. Chem. Soc. 2002, 124, 13533.
44. See, for example: (a) Andrieux, C. P.; Le Gorande, A.; Saveant, J.-M. J. Am. Chem. Soc. 1992, 114, 6892. (b) Grimshaw, J.; Langan, J. R.; Salmon, G. A. J. Chem. Soc., Faraday Trans 1994, 90, 75. (c) Andrieux, C. P.; Robert, M.; Saeva. F. D.; Saveant, J.-M. J. Am. Chem. Soc. 1994, 116, 7864. (d) Saveant, J.-M. Adv. Electron-Transfer Chem. 1994, 4, 53. (e) Adcock, W.; Andrieux, C. P.; Clark, C. I.; Neudeck, A.; Saveant, J.-M.; Tardy, C. J. Am. Chem. Soc. 1995, 117, 8285. (f) Andrieux, C. P.; Saveant, J.-M.; Tallec, A.; Tardivel, R.; Tardy, C. J. Am. Chem. Soc. 1997, 119, 2420. (g) Andrieux, C. P.; Saveant, J.-M.; Tardy, C. J. Am. Chem. Soc. 1997, 119, 11546. (h) Zhong, D.; Zewail, A. H. Proc. Natl. Acad Sci. U.S.A. 1999, 96, 2602. (i) Costentin, C.; Hapiot, P.; Medebielle, M.; Saveant, J.-M. J. Am. Chem. Soc. 2000, 122, 5623. (j) Pause, L.; Robert, M.; Saveant, J.-M. J. Am. Chem. Soc. 2000, 122, 9829. (k) Soriano, A.; Silla, E.; Tunon, I. J. Chem. Phys. 2002, 116, 6102. (l) Antonello, S.; Crisma, M.; Formaggio, F.; Moretto, A.; Taddei, F.; Toniolo, C.; Maran, F. J. Am. Chem. Soc. 2002, 124, 11503. (m) Cardinale, A.; Isse, A. A.; Gennaro, A.; Robert, M.; Saveant, J.-M. J. Am. Chem. Soc. 2002, 124, 13533.
45. See, for example: (a) Andrieux, C. P.; Le Gorande, A.; Saveant, J.-M. J. Am. Chem. Soc. 1992, 114, 6892. (b) Grimshaw, J.; Langan, J. R.; Salmon, G. A. J. Chem. Soc., Faraday Trans 1994, 90, 75. (c) Andrieux, C. P.; Robert, M.; Saeva. F. D.; Saveant, J.-M. J. Am. Chem. Soc. 1994, 116, 7864. (d) Saveant, J.-M. Adv. Electron-Transfer Chem. 1994, 4, 53. (e) Adcock, W.; Andrieux, C. P.; Clark, C. I.; Neudeck, A.; Saveant, J.-M.; Tardy, C. J. Am. Chem. Soc. 1995, 117, 8285. (f) Andrieux, C. P.; Saveant, J.-M.; Tallec, A.; Tardivel, R.; Tardy, C. J. Am. Chem. Soc. 1997, 119, 2420. (g) Andrieux, C. P.; Saveant, J.-M.; Tardy, C. J. Am. Chem. Soc. 1997, 119, 11546. (h) Zhong, D.; Zewail, A. H. Proc. Natl. Acad Sci. U.S.A. 1999, 96, 2602. (i) Costentin, C.; Hapiot, P.; Medebielle, M.; Saveant, J.-M. J. Am. Chem. Soc. 2000, 122, 5623. (j) Pause, L.; Robert, M.; Saveant, J.-M. J. Am. Chem. Soc. 2000, 122, 9829. (k) Soriano, A.; Silla, E.; Tunon, I. J. Chem. Phys. 2002, 116, 6102. (l) Antonello, S.; Crisma, M.; Formaggio, F.; Moretto, A.; Taddei, F.; Toniolo, C.; Maran, F. J. Am. Chem. Soc. 2002, 124, 11503. (m) Cardinale, A.; Isse, A. A.; Gennaro, A.; Robert, M.; Saveant, J.-M. J. Am. Chem. Soc. 2002, 124, 13533.
46. (a) Maslak, P.; Kula, J.; Chateauneuf, J. E. J. Am. Chem. Soc. 1991, 113, 2304.
47. (b) Zou, C.; Miers, J. B.; Ballew, R. M.; Dlott, D. D.; Schuster, G. B. J. Am. Chem. Soc. 1991, 113, 7823.
48. (c) Perrier, S.; Sankararaman, S.; Kochi, J. K. J. Chem. Soc., Perkin Trans. 2 1993, 825.
49. (d) Lucia, L. A.; Wang, Y.; Nafisi, K.; Netzel, T. L.; Schanze, K. S. J. Phys. Chem. 1995, 99, 11801.
50. (e) Maslak, P.; Narvaez, J. N.; Vallombroso, T. M., Jr. J. Am. Chem. Soc. 1995, 117, 12373.
51. (f) Hassoon, S.; Sarker, A.; Polykarpov, A. Y.; Rodgers, M. A. J.; Neckers, D. C. J. Phys. Chem. 1996, 100, 12386.
52. (g) Bockman, T. M.; Hubig, S. M.; Kochi, J. K. J. Org. Chem. 1997, 62, 2110.
53. (h) Bockman, T. M.; Hubig, S. M.; Kochi, J. K. J. Am. Chem. Soc. 1998, 120, 6542.
54. (i) Rasmusson, M.; Akesson, E.; Eberson, L.; Sundstrom, V. J. Phys. Chem. 2001, 105, 2027.
55. (j) Nath, S.; Singh, A. K.; Palit, D. K.; Sapre, A. V.; Mittal, J. P. J. Phys. Chem. A 2001, 105, 7151.
56. For a summary, see ref 4d.
57. (a) Popielarz, R.; Arnold, D. R. J. Am. Chem. Soc. 1990, 112, 3068.
58. (b) Maslak, P.; Vallombroso, T. M.; Chapman, W. H., Jr.; Narvaez, J. N. Angew. Chem., Int. Ed. Engl. 1994, 33, 73.
59. (c) Wayner, D. D. M.; Parker, V. D. Acc. Chem. Res. 1993, 26, 287.
60. (a) Neta, P.; Behar, D. J. Am. Chem. Soc. 1980, 102, 4798.
61. (b) Neta, P.; Behar, D. J. Am. Chem. Soc. 1981, 103, 103.
62. (c) Behar, D.; Neta, P. J. Am. Chem. Soc. 1981, 103, 2280.
63. (d) Norris, R. K.; Barker, S. D.; Neta, P. J. Am. Chem. Soc. 1984, 106, 3140.
64. (e) Kimura, N.; Takamuku, S. Bull. Chem. Soc. Jpn. 1986, 59, 3653.
65. (f) Kimura, N.; Takamuku, J. Am. Chem. Soc. 1995, 117, 8023.
66. (a) Shaik, S.; Danovich, D.; Sastry, G. N.; Ayala, P. Y.; Schlegel, H. B. J. Am. Chem. Soc. 1997, 119, 9237.
67. (b) Robert, M.; Saveant. J.-M. J. Am. Chem. Soc. 2000, 122, 514.
68. Eberson, L. Acta Chem. Scand. 1999, 53, 751.
69. Wang, X.; Saeva, F. D.; Kampmeier, J. A. J. Am. Chem. Soc. 1999, 121, 4364.
70. Pause, L.; Robert, M.; Saveant, J.-M. ChemPhysChem 2000, 1, 199.
71. These ideas are discussed in many papers from the Saveant group, including refs 4c,d.g,j,m and (a) Andrieux, C. P.; Merz, A.; Saveant J.-M. J. Am. Chem. Soc. 1985, 107, 6097. (b) Constentin, C.; Hapiot, P.; Medebielle, M.; Saveant, J.-M. J. Am. Chem. Soc. 1999, 121, 4451, (c) Pause, L.; Robert, M.; Saveant, J.-M. J. Am. Chem. Soc. 1999, 121, 7158. (d) Constentin, C.; Robert, M.; Saveant, J.-M. J. Phys. Chem. 2000, 104, 7492.
72. These ideas are discussed in many papers from the Saveant group, including refs 4c,d.g,j,m and (a) Andrieux, C. P.; Merz, A.; Saveant J.-M. J. Am. Chem. Soc. 1985, 107, 6097. (b) Constentin, C.; Hapiot, P.; Medebielle, M.; Saveant, J.-M. J. Am. Chem. Soc. 1999, 121, 4451, (c) Pause, L.; Robert, M.; Saveant, J.-M. J. Am. Chem. Soc. 1999, 121, 7158. (d) Constentin, C.; Robert, M.; Saveant, J.-M. J. Phys. Chem. 2000, 104, 7492.
73. These ideas are discussed in many papers from the Saveant group, including refs 4c,d.g,j,m and (a) Andrieux, C. P.; Merz, A.; Saveant J.-M. J. Am. Chem. Soc. 1985, 107, 6097. (b) Constentin, C.; Hapiot, P.; Medebielle, M.; Saveant, J.-M. J. Am. Chem. Soc. 1999, 121, 4451, (c) Pause, L.; Robert, M.; Saveant, J.-M. J. Am. Chem. Soc. 1999, 121, 7158. (d) Constentin, C.; Robert, M.; Saveant, J.-M. J. Phys. Chem. 2000, 104, 7492.
74. These ideas are discussed in many papers from the Saveant group, including refs 4c,d.g,j,m and (a) Andrieux, C. P.; Merz, A.; Saveant J.-M. J. Am. Chem. Soc. 1985, 107, 6097. (b) Constentin, C.; Hapiot, P.; Medebielle, M.; Saveant, J.-M. J. Am. Chem. Soc. 1999, 121, 4451, (c) Pause, L.; Robert, M.; Saveant, J.-M. J. Am. Chem. Soc. 1999, 121, 7158. (d) Constentin, C.; Robert, M.; Saveant, J.-M. J. Phys. Chem. 2000, 104, 7492.
75. Lorance, E. D.; Kramer, W. H.; Gould, I. R. J. Am. Chem. Soc. 2002, 124, 15225.
76. See also similar work by Kochi et al.: (a) Lee, K. Y.; Kochi, J, K. J. Chem. Soc., Perkin Trans. 2 1992, 1011. (b) Bookman, T. M.; Lee, K. Y.; Kochi, J, K. J. Chem. Soc., Perkin Trans. 2 1992, 1581.
77. See also similar work by Kochi et al.: (a) Lee, K. Y.; Kochi, J, K. J. Chem. Soc., Perkin Trans. 2 1992, 1011. (b) Bookman, T. M.; Lee, K. Y.; Kochi, J, K. J. Chem. Soc., Perkin Trans. 2 1992, 1581.
78. (a) Salem, L. Electrons In Chemical Reactions; Wiley-Interscience: New York, 1982.
79. (b) Michl, J.; Bonacic-Koutecky, V. Electronic Aspects of Organic Photochemistry; Wiley-Interscience: New York, 1990.
80. (c) Shaik, S. S.; Schlegel, H. B.; Wolfe, S. Theoretical Aspects of Physical Organic Chemistry; Wiley: New York, 1992.
81. (d) Pross, A. Theoretical and Physical Principles of Organic Chemistry; Wiley: New York, 1995.
82. (a) Pearson, R. G. Symmetry Rules for Chemical Reactions; Wiley: New York, 1976; Chapter 5.
83. (b) Reference 16b, Chapter 3.
84. (a) Laage, D.; Burghardt, I.; Sommerfeld, T.; Hynes, J. T. ChemPhysChem 2003, 4, 61.
85. (b) Laage, D.; Burghardt, I.; Sommerfeld, T.; Hynes, J. T. J. Phys. Chem. A 2003, 107, 11271.
86. (c) Burghardt, I.; Laage, D.; Hynes, James T. J. Phys. Chem. A 2003, 107, 11292.
87. 1.
88. (a) Gould, I. R.; Young, R. H.; Farid, S. J. Phys. Chem. 1991, 95, 2068.
89. (b) Gould, I. R.; Young, R. H.; Farid, S. In Photochemical Processes in Organized Molecular Systems; Honda, K., Ed.; Elsevier: New York, 1991.
90. (c) Gould, I. R.; Mueller, J. L.; Farid, S. Z. Phys. Chem. (Munich) 1991, 170, 143.
91. (d) Gould, I. R.; Noukakis, D.; Gomez-Jahn, L.; Young, R. H.; Goodman, J. L.; Farid, S. Chem. Phys. 1993, 176, 439.
92. (e) Arnold, B. R.; Noukakis, D.; Farid, S.; Goodman, J. L.; Gould, I. R. J. Am. Chem. Soc. 1995, 117, 4399.
93. (f) Gould, I. R.; Farid, S. Acc. Chem. Res. 1996, 29, 522.
94. Sakomura, M.; Lin, S.; Moore, T. A.; Moore, A. L.; Gust, D.; Fujihira, M. J. Phys. Chem. A 2002, 106, 2218.
95. Gould, I. R.; Ege, D.; Moser, J. E.; Farid, S. J. Am. Chem. Soc. 1990, 112, 4290.
96. (a) Johnson, A. E.; Levinger, N. E.; Kliner, D. A. V.; Torainaga, K.; Barbara, P. F. Pure Appl. Chem. 1992, 64, 1219.
97. (b) Zeglinski, D. M.; Waldeck, D. H. J. Phys. Chem. 1988, 92, 692.
98. (c) Maroncelli, M. J. Mol. Liq. 1993, 57, 1.
99. (d) Fleming, G. R.; Cho, M. Annu. Rev. Phys. Chem. 1996, 47, 109.
100. (e) Chang, Y. J.; Simon, J. D. Springer Ser. Chem. Phys. 1996, 62, 253.
101. (f) Cramer, C. J.; Truhlar, D. G. Chem. Rev. 1999, 99, 2161.
102. -et that has a small distribution in values.
103. Yamaguchi, S.; Hamaguchi, H.-O. Appl. Spectrosc. 1995, 49, 1513.
104. This corresponds to the frequency of the normal mode that most approximates the N-O stretch from a B3PW91/6-31+G* computation on 7. Details of these computations are given in: Lorance, E. D.; Hendrickson, K.; Could, I. R. J. Org. Chem. Submitted for publication.