Kinetics of the reduction of dialkyl peroxides. New insights into the dynamics of dissociative electron transfer

Journal of the American Chemical Society

Volumn 121, Issue 31, 1999, Pages 7239-7248

  Donkers, Robert L ^a   Maran, Flavio ^b   Wayner, Danial D M ^c   Workentin, Mark S ^a  

^a UNIVERSITY OF WESTERN ONTARIO   (Canada)

^b UNIVERSITY OF PADOVA   (Italy)

^c NATIONAL RESEARCH COUNCIL CANADA   (Canada)

Author keywords

[No Author keywords available]

Indexed keywords

PEROXIDE;

ARTICLE; DISSOCIATION; ELECTROCHEMICAL ANALYSIS; ELECTRON TRANSPORT; KINETICS; MOLECULAR DYNAMICS; STEREOCHEMISTRY; TEMPERATURE; THERMODYNAMICS;

EID: 0033546675     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja9906148     Document Type: Article

References (65)

1. Issued as NRCC Publication No. 42182.
2. Savéant, J.-M. Adv. Phys. Org. Chem. 1990, 26, 1.
3. Savéant, J.-M. Acc. Chem. Res. 1993, 26, 455.
4. (a) Saeva, F. D. In Topics in Current Chemistry; Mattay, J., Ed.; Springer-Verlag: Berlin, 1990; Vol. 156, p 59.
5. (b) Schuster, G. B. In Advances in Electron Transfer Chemistry; Mariano, P. S., Ed.; JAI Press: Greenwich, CT, 1991; Vol. 1, p 163.
6. (c) Maslak, P. In Topics in Current Chemistry; Mattay, J., Ed.; Springer-Verlag: Berlin, 1993; Vol. 168, p 1.
7. (d) Gaillard, E. R.; Whitten, D. G. Acc. Chem. Res. 1996, 29, 292.
8. Savéant, J.-M. In Advances in Electron Transfer Chemistry; Mariano, P. S., Ed.; JAI Press: Greenwich, CT, 1994; Vol. 4, p 53.
9. Savéant, J.-M. J. Am. Chem. Soc. 1987, 109, 6788.
10. Marcus, R. A.; Sutin, N. Biochim. Biophys. Acta 1985, 811, 265.
11. Antonello, S.; Musumeci, M.; Wayner, D. D. M.; Maran, F. J. Am. Chem. Soc. 1997, 119, 9541.
12. (a) Workentin, M. S.; Donkers. R. L. J. Am. Chem. Soc. 1998, 120, 2664.
13. (b) Donkers, R. L.; Workentin, M. S. J. Phys. Chem. B 1998, 102, 4061.
14. Workentin, M. S.; Maran, F.; Wayner, D. D. M. J. Am. Chem. Soc. 1995, 117, 2120.
15. Andrieux, C. P.; Savéant, J.-M.; Tardy, C. J. Am. Chem. Soc. 1998, 120, 4167.
16. (a) German, E. D.; Kuznetsov, A. M. J. Phys. Chem. 1994, 98, 6120.
17. (b) German, E. D.; Kuznetsov, A. M.; Tikhomirov, V. A. J. Phys. Chem. 1995, 99, 9095.
18. Severin, M. G.; Arévalo, M. C.; Maran, F.; Vianello, E. J. Phys. Chem. 1993, 97, 150.
19. Foglia, T. A.; Silbert, L. S. Synthesis 1992, 545.
20. Imbeaux, J. C.; Savéant, J.-M. J. Electroanal. Chem. 1973, 44, 169.
21. Curtis, N.; Donkers, R. L.; Leaist, D. G.; Maran, F.; Workentin, M. S. Manuscript in preparation.
22. (a) Nicholson, R. S.; Shain, I. Anal. Chem. 1964, 36, 706.
23. (b) Bard, A. J.; Faulkner, L. R. Electrochemical Methods, Fundamentals and Applications; Wiley: New York, 1980.
24. (a) Bordwell, F. G. Acc. Chem. Res. 1988, 21, 456.
25. (b) Maran, F.; Celadon, D.; Severin, M. G.; Vianello, E. J. Am. Chem. Soc. 1991, 113, 9320.
26. 20 and thus with the Stokes-Einstein relation. Analogous results are obtained with the other peroxides. This is relevant because it means that the number of exchanged electrons is the same in both solvents, within error.
27. Riddick, J. A.; Bunger, W. B.; Sakano, T. K. Organic Solvents, Physical Properties and Methods of Purification, 4th ed.; Weissberger, A., Ed.; Techniques of Chemistry II; John Wiley and Sons: New York, 1986.
28. Organic Peroxides; Ando, W., Ed.; Wiley: New York, 1992.
29. (a) Andrieux, C. P.; Blocman, C.; Dumas-Bouchiat, J. M.; M'Halla, F.; Savéant J.-M. J. Electroanal. Chem. 1980, 113, 19.
30. (b) Andrieux, C. P.; Savéant J.-M. J. Electroanal. Chem. 1986, 205, 43.
31. Avila, D. V.; Brown, C. E.; Ingold, K. U.; Lusztyk, J. J. Am. Chem. Soc. 1993, 115, 466.
32. Kjær, N. T.; Lund, H. Acta Chem. Scand. 1995, 49, 848.
33. Antonello, S.; Maran, F. J. Am. Chem. Soc. 1997, 119, 12595.
34. Antonello, S.; Maran, F. J. Am. Chem. Soc. 1998, 120, 5713.
35. Wayner, D. D. M.; Parker, V. D. Acc. Chem. Res. 1993, 26, 287.
36. Baldwin, A. C. In The Chemistry of Peroxides; Patai, S., Ed.; Wiley: New York, 1983; p 97.
37. Benson, S. W. Thermochemical Kinetics, 2nd ed.; Wiley: New York, 1976.
38. Wong, S. K. Int. J. Chem. Kinet. 1981, 13, 433.
39. (a) Batt, L.; Benson, S. W. J. Chem. Phys. 1962, 36, 895.
40. (b) Batt, L.; Christie, K.; Milne, R. T.; Summers, A. Int. J. Chem. Kinet. 1974, 6, 877.
41. (c) Lewis, D. K. Can. J. Chem. 1976, 54, 581.
42. Matsugo, S.; Saito, I. In Organic Peroxides; Ando, W., Ed.; Wiley: New York, 1992.
43. Denisov, E. T. In Liquid Phase Reaction Rate Constants; Plenum: New York, 1974.
44. Benson, S. W. J. Chem. Phys. 1964, 40, 1007.
45. Walker, R. F.; Phillips, L. J. Chem. Soc. A 1968, 2103.
46. In principle it is possible to generate a constant concentration of these radicals and to study their reduction by photomodulated voltammetry, as previously done with many other radicals (Wayner, D. D. M.; McPhee, D. J.; Griller, D. J. Am. Chem. Soc. 1988, 110, 132), but the electrochemistry is ill-defined.
47. NIST Standard Reference Database 25; NIST Structures and Properties Database and Estimation Program, U.S. Department of Commerce: Gaithersburg, MD, 1991.
48. Izutzu, K. Acid - Base Dissociation Constants in Dipolar Aprotic Solvents; Chemical Data Series 35; Blackwell Scientific Publications: Oxford, 1990.
49. ox, = 0.08 V).
50. Parker, V. D.; Tilset, M.; Hammerich, O. J. Am. Chem. Soc. 1987, 109, 7905 and references therein.
51. (a) Lund, H.; Daasbjerg, K.; Lund, T.; Pedersen, S. U. Acc. Chem Res. 1995, 28, 313.
52. (b) Lund, H.; Daasbjerg, K.; Lund, T.; Occhialini, D.; Pedersen, S. U. Acta Chem. Scand. 1997, 51, 135.
53. ○ ≈ 0.5, as expected for any moderately driven activated process.
54. Kojima, H.; Bard, A. J. J. Am. Chem. Soc. 1975, 97, 6317.
55. Eberson, L. Adv. Phys. Org. Chem. 1982, 18, 79.
56. tr to the ionic radius (the range of values is from -87 meV/K for fluoride to -107 meV/K for thiocyanate).
57. -1, as used by Savéant in his treatment of tert-butyl bromide, increases the predicted rate constants by 1.5 orders of magnitude, so they appear to overlap the closed circles in Figure 2.
58. Newton, M. D.; Sutin, N. Annu. Rev. Phys. Chem. 1984, 35, 437.
59. 2m] (dr/dα).
60. Sutin, N. Prog. Inorg. Chem. 1983, 30, 441.
61. Savéant, J.-M. J. Am. Chem. Soc. 1992, 114, 10595.
62. Lund, T.; Lund, H. Acta Chem. Scand. 1986, B40, 470.
63. Lin-Vien, D.; Colthup, N. B.; Fateley, W. G.; Grasselli, J. G. The Handbook of Infrared and Roman Characteristic Frequencies of Organic Molecules; Academic Press: Toronto, 1991.
64. Marcus, R. A. Acta Chem. Scand. 1998, 52, 858.
65. Daasbjerg, K.; Jensen, H.; Benassi, R.; Taddei, F.; Antonello, S.; Gennaro, A.; Maran, F. J. Am. Chem. Soc. 1999, 121, 1750.