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Atom transfer mechanisms in oxidation processes

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Abstract

The emphasis placed on electron transfer in connection with oxidation reactions has often resulted in these processes being considered as a group apart from the main class of chemical reactions. Although some oxidations, for example certain exchange reactions between ions in solution, can be reasonably described as electron transfer processes, there are very many other oxidations, whose mechanisms are much better described in the familiar terms of modern organic chemistry.

The use of isotopes as tracers has shown, that many oxidations proceed with transfer of atoms or groups from oxidant to reductant andvice versa; the use of the kinetic isotope effect has shown that such transfer is seldom an incidental process, but is almost always a part of the slow step of the reaction. In this paper, oxidations involving the transfer of such species as oxygen atoms, hydride ions, hydrogen atoms, chlorine atoms, and hydroxyl radicals are discussed in terms of mechanism. An attempt is made to show that a graded series of mechanisms is possible ranging from what appear to be pure electron transfer processes at one end to certain atom transfer processes at the other. The latter group belong, in fact, in the familiar realm of ordinary chemical raactions, in which strong bonds are being broken and formed in the activated complex.

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Literatur

  1. L. S. Levitt, J. org. Chem.20, 1297 (1955).

    CAS  Google Scholar 

  2. C. K. Ingold, Chem. Rev.15, 266 (1934).

    Google Scholar 

  3. M. Anbar andH. Taube, J. Amer. chem. Soc.80, 1073 (1958).

    CAS  Google Scholar 

  4. A. C. Wahl andC. P. Deck, J. Amer. chem. Soc.76, 4054 (1954).

    CAS  Google Scholar 

  5. J. C. Shepherd andA. C. Wahl, J. Amer. chem. Soc.79, 1020 (1957).

    Google Scholar 

  6. E. Eichler andA. C. Wahl, J. Amer. chem. Soc.80, 4145 (1958).

    CAS  Google Scholar 

  7. R. A. Marcus, Trans. N. Y. Acad. Sci.19, 432 (1957).

    Google Scholar 

  8. W. F. Libby, J. phys. Chem.56, 863 (1952).

    CAS  Google Scholar 

  9. F. Basolo andR. G. Pearson,Mechanisms of Inorganic Reactions (John Wiley & Son, New York 1958), p. 303.

    Google Scholar 

  10. B. J. Zwolinski, R. J. Marcus, andH. Eyring, Chem. Rev.55, 157 (1955).

    CAS  Google Scholar 

  11. R. A. Marcus, J. chem. Phys.26, 872 (1957).

    CAS  Google Scholar 

  12. F. C. Adam andS. Weissman, J. Amer. chem. Soc.80, 1518 (1958).

    CAS  Google Scholar 

  13. R. E. Kirk andA. W. Browne, J. Amer. chem. Soc.50, 337 (1928).

    CAS  Google Scholar 

  14. W. C. E. Higginson andJ. W. Marshall, J. chem. Soc.1957, 447.

  15. W. C. E. Higginson, D. Sutton, andP. Wright, J. chem. Soc.1953, 1380.

  16. J. Halpern, Can. J. Chem.37, 148 (1959).

    CAS  Google Scholar 

  17. F. H. Westheimer,The Mechanisms of Enzyme Action (Ed.W. D. McElroy andB. Glass, John Hopkins Univ. Press) p. 321.

  18. R. Stewart andR. Van Der Linden, unpublished results.

  19. K. B. Wiberg andR. Stewart, J. Amer. chem. Soc.78, 1214 (1956).

    CAS  Google Scholar 

  20. J. Halperin andH. Taube, J. Amer. chem. Soc.74, 375 (1952).

    CAS  Google Scholar 

  21. J. Halperin andH. Taube, J. Amer. chem. Soc.74, 380 (1952).

    CAS  Google Scholar 

  22. A. Cresswell, U. S. Patent 2,751,374 (1956).

  23. A. Hill, U. S. Patent 2,673,192 (1954).

  24. E. H. Gleason, G. Mino, andW. M. Thomas, J. phys. Chem.61, 444 (1957).

    Google Scholar 

  25. K. B. Wiberg andR. Stewart, J. Amer. chem. Soc.77, 1788 (1955).

    Google Scholar 

  26. F. H. Westheimer, Chem. Rev.45, 419 (1950).

    Google Scholar 

  27. F. H. Westheimer andN. Nicolaides, J. Amer. chem. Soc.71, 25 (1949).

    CAS  Google Scholar 

  28. F. Holloway, M. Cohen, andF. H. Westheimer, J. Amer. chem. Soc.73, 65 (1951).

    CAS  Google Scholar 

  29. L. Kaplan, J. Amer. chem. Soc.77, 5469 (1955).

    Google Scholar 

  30. J. Rocek andJ. Krupicka, Chem. & Ind.1957, 1668.

  31. G. Wagner, J. Russ. phys. chem. Soc.27, 219 (1895).

    Google Scholar 

  32. J. Boeseken, Rec. Trav. chim. Pays-Bas40, 553 (1921).

    CAS  Google Scholar 

  33. K. B. Wiberg andK. A. Saegebarth, J. Amer. chem. Soc.79, 2822 (1957).

    CAS  Google Scholar 

  34. K. B. Wiberg andK. A. Saegebarth, J. Amer. chem. Soc.79, 6256 (1957).

    CAS  Google Scholar 

  35. W. von E. Doering andE. Dorfman, J. Amer. chem. Soc.75, 5595 (1953).

    CAS  Google Scholar 

  36. E. Mosettig andL. Jovanovic, Mh. Chem.53, 427 (1929).

    Google Scholar 

  37. L. P. Hammett,Physical Organic Chemistry (McGraw Hill Book Co., N.Y. 1940), p. 350.

    Google Scholar 

  38. R. B. Woodward, N. L. Wendler andF. J. Brutschy, J. Amer. chem. Soc.67, 1425 (1945).

    CAS  Google Scholar 

  39. S. J. Angyal andR. C. Rassack, J. chem. Soc.1949 (2700).

  40. M. L. Moore inOrganic Reactions, Vol. V (R. Adams, Ed., John Wiley and Sons, New York 1949), p. 301.

    Google Scholar 

  41. W. von E. Doering andT. C. Aschner, J. Amer. chem. Soc.75, 393 (1953).

    CAS  Google Scholar 

  42. G. E. Dunn andJ. Warkentin, Canad. J. Chem.34, 75 (1956).

    CAS  Google Scholar 

  43. R. Stewart, J. Amer. chem. Soc.79, 3057 (1957).

    CAS  Google Scholar 

  44. M. Avranoff andY. Springzak, J. Amer. chem. Soc.80, 493 (1958).

    Google Scholar 

  45. P. D. Bartlett, F. E. Condon, andA. Schneider, J. Amer. chem. Soc.66, 1531 (1954).

    Google Scholar 

  46. T. A. Geissman inOrganic Reactions, Vol. II (R. Adams, Ed. John Wiley and Sons, New York 1944), p. 96.

    Google Scholar 

  47. K. B. Wiberg, J. Amer. chem. Soc.76, 5371 (1954).

    CAS  Google Scholar 

  48. D. Dvornik andO. E. Edwards, Proc. chem. Soc.1958, 280.

  49. P. D. Bartlett andJ. D. McCollum, J. Amer. chem. Soc.78, 1441 (1956).

    CAS  Google Scholar 

  50. R. Stewart, Canad. J. Chem.35, 766 (1957).

    CAS  Google Scholar 

  51. N. J. Leonard andR. R. Sauers, J. Amer. chem. Soc.79, 6210 (1957).

    CAS  Google Scholar 

  52. D. F. de Tar andT. Kosuge, J. Amer. chem. Soc.80, 6072 (1958).

    Google Scholar 

  53. H. J. Dauben, F. A. Gadecki, K. M. Harmon, andD. L. Pearson, J. Amer. chem. Soc.79, 4557 (1957).

    CAS  Google Scholar 

  54. K. Clusius andE. Eppenberger, Helv. chim. Acta38, 1843 (1955).

    CAS  Google Scholar 

  55. J. Halpern, Quart. Revs.10, 463 (1956).

    CAS  Google Scholar 

  56. M. F. Hawthorne andE. S. Lewis, J. Amer. chem. Soc.80, 2496 (1958).

    Google Scholar 

  57. E. S. Lewis andM. C. R. Symons, Quart. Rev.12, 230 (1958).

    CAS  Google Scholar 

  58. H. Taube andH. Myers, J. Amer. chem. Soc.76, 2103 (1954).

    CAS  Google Scholar 

  59. H. Taube, J. Amer. chem. Soc.77, 4481 (1955).

    CAS  Google Scholar 

  60. R. K. Murmann, H. Taube, andF. A. Posey, J. Amer. chem. Soc.79, 262 (1957).

    CAS  Google Scholar 

  61. H. Taube, Canad. J. Chem.37, 129 (1959).

    CAS  Google Scholar 

  62. C. K. Ingold,Structure and Mechanism in Organic Chemistry (Cornell University Press, Ithaca, N. Y. 1953), p. 205.

    Google Scholar 

  63. W. A. Waters inOrganic Chemistry, Vol. IV (H. Gilman, Ed., John Wiley and Sons, New York 1953), p. 1120.

    Google Scholar 

  64. J. Hudis andR. W. Dodson, J. Amer. chem. Soc.78, 911 (1956).

    CAS  Google Scholar 

  65. A. E. Ogard andH. Taube, J. Amer. chem. Soc.80, 1084 (1958).

    CAS  Google Scholar 

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Authors
  1. R. Stewart
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Additional information

Contribution from Department of Chemistry, University of British Columbia, Vancouver. — Presented at the Organic Chemistry Symposium of the Chemical Institute of Canada, Ottawa, Dec. 8–9, 1958.

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Stewart, R. Atom transfer mechanisms in oxidation processes. Experientia 15, 401–406 (1959). https://doi.org/10.1007/BF02158977

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