The role and relevance of the transfer coefficient α in the study of dissociative electron transfers: Concepts and examples from the electroreduction of perbenzoates

Journal of the American Chemical Society

Volumn 121, Issue 41, 1999, Pages 9668-9676

  Antonello, Sabrina ^a   Maran, Flavio ^a  

^a UNIVERSITY OF PADOVA   (Italy)

Author keywords

[No Author keywords available]

Indexed keywords

CHEMICAL COMPOUND; PEROXIDE;

ARTICLE; CHEMICAL ANALYSIS; CHEMICAL BINDING; CYCLIC POTENTIOMETRY; ELECTRON TRANSPORT; REACTION ANALYSIS; REDUCTION; TEMPERATURE;

EID: 0032756371     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja991407a     Document Type: Article

References (63)

1. (a) Savéant, J.-M. Adv. Phys. Org. Chem. 1990, 26, 1.
2. (b) Savéant, J.-M. Acc. Chem. Res. 1993, 26, 455.
3. Savéant, J.-M. In Advances in Electron-Transfer Chemistry; Mariano, P. S., Ed.; JAI press: Greenwich, CT, 1994; Vol. 4, p 53.
4. Schuster, G. B. In Advances in Electron-Transfer Chemistry; Mariano, P. S., Ed.; JAI Press: Greenwich, CT, 1991; Vol. 1, p 163.
5. Maslak, P. In Topics in Current Chemistry; Mattay, J., Ed.; Springer-Verlag: Berlin, 1993; Vol. 168, p 1.
6. Gaillard, E. R.; Whitten, D. G. Acc. Chem. Res. 1996, 29, 292.
7. (a) Capobianco, G.; Farnia, G.; Severin, M. G.; Vianello, E. J. Electroanal. Chem. 1984, 765, 251.
8. (b) Severin, M. G.; Arévalo, M. C.; Farnia, G.; Vianello, E. J. Phys. Chem. 1987, 91, 466.
9. (c) Arévalo, M. C.; Farnia, G.; Severin, M. G.; Vianello, E. J. Electroanal. Chem. 1987, 220, 201.
10. (d) Severin, M. G.; Farnia, G.; Vianello, E.; Arévalo, M. C. J. Electroanal. Chem. 1988, 251, 369.
11. (e) Severin, M. G.; Arévalo, M. C.; Maran, F.; Vianello, E. J. Phys. Chem. 1993, 97, 150.
12. (a) Andersen, M. L.; Mathivanan, N.; Wayner, D. D. M. J. Am. Chem. Soc. 1996, 118, 4871.
13. (b) Andersen, M. L.; Wayner, D. D. M. J. Electroanal. Chem. 1996, 412, 53.
14. (c) Andersen, M. L.; Long, W.; N.; Wayner, D. D. M. J. Am. Chem. Soc. 1997, 119, 6590.
15. (a) Andrieux, C. P.; Savéant, J.-M.; Tallec, A.; Tardivel, R.; Tardy, C. J. Am. Chem. Soc. 1996, 118, 9788.
16. (b) Andrieux, C. P., Savéant, J.-M.; Tallec, A.; Tardivel, R.; Tardy, C. J. Am. Chem. Soc. 1997, 119, 2420.
17. Savéant, J.-M. J. Am. Chem. Soc. 1987, 109, 6788.
18. (a) Andrieux, C. P.; Savéant J.-M. J. Etectroanal. Chem. 1986, 205, 43.
19. (b) Andrieux, C. P.; Robert, M.; Saeva, F. D.; Savéant J.-M. J. Am. Chem. Soc. 1994, 116, 7864.
20. (c) Andrieux, C. P.; Savéant J.-M.; Tardy, C. J. Am. Chem. Soc. 1997, 119, 11546.
21. (d) Costentin, C.; Hapiot, P.; Médebielle M.; Savéant J.-M. J. Am. Chem. Soc. 1999, 121, 4451.
22. (e) Pause, L.; Robert, M.; Savéant J.-M. J. Am. Chem. Soc. 1999, 121, 7158.
23. Antonello, S.; Maran, F. J. Am. Chem. Soc. 1997, 119, 12595.
24. (a) Eberson, L. Electron-Transfer Reactions in Organic Chemistry; Springer-Verlag: Heidelberg, 1987.
25. (b) Lund, H.; Daasbjerg, K.; Lund, L.; Pedersen, S. U. Acc. Chem. Res. 1995, 28, 313.
26. (c) Marcus, R. A. J. Phys. Chem. A 1997, 101, 4072.
27. (d) Kuznetsov, A. M. J. Phys. Chem. A 1999, 103, 1239.
28. For example, see: Williams, A. Chem. Soc. Rev. 1994, 23, 93.
29. For example, see: Marcus, R. A.; Sutin, N. Biochim. Biophys. Acta 1985, 811, 265.
30. (a) Workentin, M. S.; Maran, F.; Wayner, D. D. M. J. Am. Chem. Soc. 1995, 117, 2120.
31. (b) Denkers, R. L.; Maran, F.; Wayner, D. D. M.; Workentin, M. S. J. Am. Chem. Soc. 1999, 121, 7239.
32. Antonello, S.; Musumeci, M.; Wayner, D. D. M.; Maran, F. J. Am. Chem. Soc. 1997, 119, 9541.
33. (a) Workentin, M. S.; Donkers, R. L. J. Am. Chem. Soc. 1998, 120, 2664.
34. (b) Donkers, R. L.; Workentin, M. S. J. Phys. Chem. B 1998, 102, 4061.
35. Daasbjerg, K.; Jensen, H.; Benassi, R.; Taddei, F.; Antonello, S.; Gennaro, A.; Maran, F. J. Am. Chem. Soc. 1999, 121, 1750.
36. Benassi, R.; Taddei, F. J. Phys. Chem. A 1998, 102, 6173.
37. Benassi, R.; Taddei, F.; Antonello, S.; Maran, F. et al., manuscript in preparation.
38. German, E. D.; Kuznetsov, A. M. J. Phys. Chem. A. 1998, 102, 3668.
39. Isse, A. A.; Gennaro, A.; Maran, F. Acta Chem. Scand., in press.
40. A nonadiabatic dissociative ET theory has been developed: German, E. D.; Kuznetsov, A. M. J. Phys. Chem. 1994, 98, 6120.
41. Antonello, S.; Maran, F. J. Am. Chem. Soc. 1998, 120, 5713.
42. Preliminary data suggest that the double layer properties of glassy carbon in DMF are qualitatively similar to those of mercury: Arévalo, M. C., Maran, F., work in progress.
43. 12c,d However, as the comparison with the experimental data presented in this paper will show, the mechanism transition is conveniently describable as a simple competition problem, at least at a first level of approximation.
44. (a) Imbeaux, J. C.; Savéant, J.-M. J. Electroanal. Chem. 1973, 44, 169.
45. (b) Savéant, J.-M.; Tessier, D. J. Electroanal. Chem. 1975, 65, 57.
46. Filliatre, C.; Maillard, B.; Villenave, J. J. Thermochim. Acta 1980, 39, 195.
47. (a) Blomquist, A. T.; Berstein, J. J. Am. Chem. Soc. 1951, 73, 5546.
48. (b) Plesnicar, B.; Exner, O. Collect. Czech. Chem. Commun. 1981, 46, 490.
49. Curtis, N.; Donkers, R. L.; Isse, A. A.; Leaist, D. G.; Maran, F.; Workentin, M. S., to be published.
50. (a) Nicholson, R. S.; Shain, I. Anal. Chem. 1964, 36, 706.
51. (b) Nadjo, L.; Savéant, J.-M. J. Electroanal. Chem. 1973, 48, 113.
52. (c) Bard, A. J.; Faulkner, L. R. Electrochemical Methods, Fundamentals and Applications; Wiley: New York, 1980.
53. In particular, see: (a) Arévalo, M. C.; Farnia, G.; Severin, M. G.; Vianello, E. J. Electroanal. Chem. 1987, 220, 201. (b) Maran, F.; Roffia, S.; Severin, M. G.; Vianello, E. Electrochim. Acta 1990, 35, 81.
54. In particular, see: (a) Arévalo, M. C.; Farnia, G.; Severin, M. G.; Vianello, E. J. Electroanal. Chem. 1987, 220, 201. (b) Maran, F.; Roffia, S.; Severin, M. G.; Vianello, E. Electrochim. Acta 1990, 35, 81.
55. 28,29a
56. 11
57. B·/B- estimates were required in the present investigation.
58. See footnote 19 in ref 8b.
59. - is 0) allow one to predict that the voltammetric pattern of 1c and 1d should not be very different, despite the difference of the corresponding σ values, 0.50 and 0.66, respectively.
60. l - I(t)]/i(t)}
61. ET data obtained at different scan rates.
62. 16 derives from an extensive set of experimental data: Kojima, H.; Bard, A. J. J. Am. Chem. Soc. 1975, 97, 6317.
63. AB/A·,B-, the mechanism shifts to one in which the concerted component becomes more important than that observed at 25 °C. A similar temperature effect has been recently described (Reference 10e. We are grateful to Professor Savéant for providing us an advanced copy of the manuscript).