Single electron transfer and nucleophilic substitution. Reaction of alkyl bromides with aromatic anion radicals and low oxidation state iron porphyrins

Journal of the American Chemical Society

Volumn 110, Issue 23, 1988, Pages 7617-7625

  Lexa, Doris ^a   Saveant, Jean Michel ^a   Su, Khac Binh ^a   Wang, Dan Li ^a  

^a UNIVERSITÉ PARIS DIDEROT   (France)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 33845278996     PISSN: 00027863     EISSN: 15205126     Source Type: Journal    
DOI: 10.1021/ja00231a006     Document Type: Article

References (20)

1. (a) Lexa, D.; Mispelter, J.; Saveant, J-M. J. Am. Chem. Soc. 1981, 103, 6806. (b) Eberson, L. Electron Transfer Reactions in Organic Chemistry; Springer-Verlag: Berlin, 1987; pp 14–16. (c) Eberson, L. Acta Chem. Scand., Ser. B 1982, 36, 533.
2. 3. (b) Pross, A. Adv. Phys. Org. Chem. 1985, 21, 99. (c) Shaik, S. S. Prog. Phys. Org. Chem. 1985, 15, 197. (d) Pross, A. Acc. Chem. Res. 1985, 18, 212.
3. (a) Hush, N. S. J. Chem. Phys. 1958, 28, 962. (b) Hush, N. S. Trans. Faraday Soc. 1961, 57, 557. (c) Marcus, R. A. J. Chem. Phys. 1956, 24, 4966. (d) Marcus, R. A. Annu. Rev. Phys. Chem. 1964, 15, 155. (e) Marcus, R. A. J. Chem. Phys. 1965, 43, 679. (f) Waisman, E.; Worry, G.; Marcus, R. A. J. Electroanal. Chem. 1977, 82, 9. (g) Marcus, R. A. Faraday Discuss. Chem. Soc. 1982, 74, 7. (h) Marcus, R. A.; Sutin, N. Biochim. Biophys. Acta 1985, 811, 265.
4. (a) Sargent, C. D.; Lux, G. A. J. Am. Chem. Soc. 1968, 90, 7160. (b) Garst, J. F.; Barbas, J. T.; Barton, F. E. J. Am. Chem. Soc. 1968, 90, 7159. (c) Garst, J. F. Acc. Chem. Res. 1971, 4, 400. (d) Garst, J. F.; Barton, F. E. J. Am. Chem. Soc. 1974, 96, 223. (e) Margel, S.; Levy, M. J. Electroanal. Chem. 1974, 56, 259. (f) Lund, H.; Michel, M. A.; Simonet, J. Acta Chem. Scand., Ser B 1974, 28, 900. (g) Bank, S.; Juckett, D. A. J. Am. Chem. Soc. 1975, 97, 567. (h) Garst, J. F.; Abels, B. N. J. Am. Chem. Soc. 1975, 97, 4926. (i) Sease, W. J.; Reed, C. R. Tetrahedron Lett. 1975, 393. (j) Britton, W. E.; Fry, A. J. Anal. Chem. USSR 1975, 47, 95. (k) Simonet, J.; Michel, M. A.; Lund, H. Acta Chem. Scand., Ser B 1975, 29, 489. (1) Bank, S.; Juckett, D. A. J. Am. Chem. Soc. 1975, 97, 567. (m) Malissard, M.; Mazaleyrat, J. R.; Welvart, Z. J. Am. Chem. Soc. 1977, 99, 6933. (n) Hebert, E.; Mazaleyrat, J. P.; Welvart, Z.; Nadjo, L.; Saveant, J-M. Nouv. J. Chim. 1975, 9, 75. (o) Andrieux, C. P.; Gallardo, I.; Saveant, J-M.; Su, K. B. J. Am. Chem. Soc. 1986, 108, 638. (p) Andrieux, C. P.; Saveant, J-M.; Su, K. B. J. Phys. Chem. 1986, 90, 3815. (q) Lund, T.; Lund, H. Acta Chem. Scand., Ser B 1986, 40, 470. (r) Savéant, J-M. Mechanisms and Reactivity in Organic Electrochemistry. Recent Advances. Proceedings of the Robert A. Welsh Foundation Conferences on Chemical Research, Advances in Electrochemistry, Houston, TX, 1986; Chapter IV, pp 289–336. (s) Saveant, J-M. J. Am. Chem. Soc. 1987, 109, 6788. (t) Saveant, J-M. Bull. Soc. Chim. Fr. 1988, 225.
5. (a) Andrieux, C. P.; Dumas-Bouchiat, J. M.; Saveant, J-M. J. Electroanal. Chem. 1978, 87, 39. (b) J. Electroanal. Chem. 1978, 87, 55. (c) J. Electroanal. Chem. 1978, 88, 27. (d) Andrieux, C. P.; Blocman, C.; Savéant, J-M. J. Electroanal. Chem. 1979, 79, 413. (e) Andrieux, C, P.; Dumas-Bouchiat, J. M.; Savéant, J-M. J. Electroanal. Chem. 1970, 113, 1. (f) Saveant, J-M.; Su, K. B. J. Electroanal. Chem. 1984, 171, 341. (g) Savéant, J-M.; Su, K. B. J. Electroanal. Chem. 1985, 136, 1. (h) Nadjo, L.; Saveant, J-M.; Su, K. B. J. Electroanal. Chem. 1985, 196, 23.
6. 4o,p,6d(b) Eberson, L. Adv. Phys. Org. Chem. 1982, 18, 79. (c) Eberson, L. Chem. Ser 1982, 20, 29. (d) Reference lb, pp 122, 123.
7. (a) Nicholson, R. S.; Shain, I. Anal. Chem. 1964, 36, 706. (b) Bard, A. J.; Faulkner, L. W. Electrochemical Methods, Wiley: New York, 1980; pp 429–487. (c) Andrieux, C. P.; Saveant, J-M. Electrochemical Reactions. In Investigations of Rates and Mechanisms of Reactions; Bernasconi, C. F., Ed.; Wiley: New York, 1986; Vol. 6, 4/E, Part 2, pp 305–390.
8. 4q(b) Andrieux, C. P.; Saveant, J-M. J. Electroanal. Chem. 1970, 28, 339. (c) Andrieux, C. P.; Hapiot, H.; Savéant, J-M. J. Electroanal. Chem. 1984, 172, 49.
9. (a) This is at best a rough approximation for a liquid-phase reaction. (b) Besides the uncertainties in the evaluation of the Z factor for a liquid-phase reaction, a slightly positive activation entropy could result from the electric charge being less concentrated in the transition state than in the reactants leading to more solvent fluctuation disorder in the transition state. Bending vibration of the C-X bond in the transition state could enhance its partition function and thus contribute to increase the activation entropy. As far as colinear bond reorganization is concerned, we thus assume that the activation entropy is close to zero.
10. 16b(b) Albery, W. J.; Kreevoy, M. M. Adv. Phys. Org. Chem. 1978, 15, 87. (c) Actually methyl cation transfer reactions.
11. (a) From ref 17b-e. (b) Handbook of Chemistry and Physics, 52nd ed.; CRC: Cleveland, 1972; p E95. (c) Wagman, D. D.; Evans, W. H.; Parker, V. B.; Schumm, R. H.; Halow, I.; Bailey, S. M.; Churney, K. L.; Nuttal, R. L. J. Phys. Chem. Ref Data 1982, I1, Suppl. 2. (d) Cos, B. G.; Hedwig, G. R.; Parker, A. J.; Watts, D. W. Aust, J. Chem. 1976, 27, 677. (e) Koppenol, W. H.; Liebman, J. F. J. Phys. Chem. 1984, 88, 89.
12. Baudreau, C. A.; Caughey, W. S. Biochemistry 1968, 7, 624.
13. Momenteau, M.; Mispelter, J.; Look, B.; Bisagni, E. J. Chem. Soc., Perkin Trans, l 1983, 183.
14. Marple, L. W. Anal. Chem. 1967, 39, 865.
15. Garreau, D.; Saveant, J-M. J. Electroanal. Chem. 1972, 35, 309.
16. Crank, J. Mathematics of Diffusion; Oxford University Press: London, 1957.
17. Amatore, C.; Gareil, M.; Saveant, J-M. J. Electroanal. Chem. 1983, 147, 1.
18. N2 pathways, clearer in the first case than in the other two. (25) Symons, M. C. R. Pure Appl. Chem. 1981, 53, 223.
19. +, reaction 9 is a strongly downhill process (driving force >0.35 eV). (c) The dichlorodicyanobenzoquinone anion radical is an example of mixed kinetic control by reactions 8 and 9, owing to a smaller driving force for the electron transfer step (0.2 eV). (d) Andrieux, C. P.; Merz, A.; Savéant, J-M. J. Am. Chem. Soc. 1985, 107, 6097.
20. RNl Mechanism, ACS Monograph 178; The American Chemical Society: Washington, D.C., 1983.