Skip to content
1887
Volume 35, Issue 3
  • ISSN: 0032-1400

Abstract

A metal catalysed, electrophilic approach to methane oxidation is discussed. This involves the oxidation of methane to the corresponding methyl ester in trifluoroacetic acid; the oxidant is hydrogen peroxide and the catalyst is the palladium(II) ion. The latter species activates methane by the electrophilic cleavage of a C-H bond, and then acts as a two-electron oxidant towards the resultant metal-bound methyl group. The hydrogen peroxide reoxidises palladium(0) back to palladium(II)

Loading

Article metrics loading...

/content/journals/10.1595/003214091X353126132
1991-01-01
2024-12-23
Loading full text...

Full text loading...

/deliver/fulltext/pmr/35/3/pmr0035-0126.html?itemId=/content/journals/10.1595/003214091X353126132&mimeType=html&fmt=ahah

References

  1. J. March, “Advanced Organic Chemistry”, Wiley, New York, 1985, p. 620 and references therein. [Google Scholar]
  2. G. Olah, Ace. Chem. Res., 1987, 20, 422 [Google Scholar]
  3. A. E. Shilov, (a)“Activation of Saturated Hydrocarbons by Transition Metal Compounds”, Reidel, Dordrecht, 1984, Chapter V; [Google Scholar]
  4. L. A. K, V. V. Lavrushko, Yu. S. Misharin, A. P. f Moravskii, A. E. Shilov, (b)Nouv. J. Chim., 1983, 7, 729; [Google Scholar]
  5. Yu. V. Geletii, A. E. Shilov, (c)Kinet. Ratal, 1983, 24, 486 [Google Scholar]
  6. N. M. Emanuel, E. T. Denisov, Z. K. Maizus, Review, (a)“Liquid-Phase Oxidation of Hydrocarbons”, Plenum, New York, 1967; [Google Scholar]
  7. N. M. Emanuel, G. E. Zaikov, Z. K. Maizus, (b)“Oxidation of Organic Compounds”, Pergamon, New York, 1984 [Google Scholar]
  8. Reviews: (a)op. cit., (Ref. 3a), Chapter IV; [Google Scholar]
  9. R.A. Sheldon, J. K. Kochi, (b)“Metal-Catalyzed Oxidation of Organic Compounds”, Academic, New York, 1981 [Google Scholar]
  10. J. T. Groves, Reviews: (a)J. Chem. Ed., 1985, 62, 928; [Google Scholar]
  11. F. P. Guegerich, T. L. Macdonald, (b)Acc. Chem. Res., 1984, 17, 9 [Google Scholar]
  12. B. Meunier, Leading references for related oxidative functionalisation of alkanes by metalloporphyrins: (a)Bull. Soc.Chim.Fr., 1986, 4, 578; [Google Scholar]
  13. D. Mansuy, (b)Pure Appl. Chem., 1987, 59, 759; [Google Scholar]
  14. C. L., (c)Hill, Adv. Oxygenated Process., 1988, 1, 1; [Google Scholar]
  15. C. L. Hill, (d)” Activation and Functionalization of Alkanes”, John Wiley, New York, 1989 [Google Scholar]
  16. C. T. Hou, Reviews: (a)“Methylotrophs: Microbiology, Biochemistry and Genetics”, CRC Press, Boca Raton, 1984; [Google Scholar]
  17. C. T. Hou, (b)Biotechnol. Genet. Eng. Rev., 1986, 4, 145; [Google Scholar]
  18. J. Green, H. Dalton, Mechanism: (c)J. Biol. Chem., 1989, 264, 17698 [Google Scholar]
  19. J. H. Lunsford, (a)Catal. Today, 1990, 6, 235; [Google Scholar]
  20. G. H. Hutchings, M. S. Scurrell, J. R. Woodhouse, (b)Chem. Soc. Rev., 1989, 18, 251; [Google Scholar]
  21. G. H. Hutchings, J. R. Woodhouse, M. S. Scurrell, (c)J. Chem. Soc, Faraday Trans. I, 1989, 85, 2507; [Google Scholar]
  22. Also see, Catal. Today, 1989, 4 [Google Scholar]
  23. T. T. Wenzel, R. G. Bergman, Leading references: (a)J. Am. Chem. Soc, 1986, 108, 4856; [Google Scholar]
  24. C. K. Ghosh, W. A. Graham, (b)J. Am. Chem. Soc, 1987, 109, 4726; [Google Scholar]
  25. M. Hackett, G. M. Whitesides, (c)J. Am. Chem. Soc, 1988, 110, 1449; [Google Scholar]
  26. T. G. P. Harper, R. S. Shinomoto, M. A. Deming, T. C. Flood, (d)J. Am. Chem. Soc, 1988, 110, 7915 [Google Scholar]
  27. J. Halpern, Inorg. Chim. Acta, 1985, 100, 41 [Google Scholar]
  28. E. Gretz, T. F. Oliver, A. Sen, (a)J. Am. Chem. Soc, 1987, 109, 8109; [Google Scholar]
  29. A. Sen, E. Gretz, T. F. Oliver, Z. Jiang, (b)New J. Chem., 1989, 13, 755; [Google Scholar]
  30. L.-C. Kao, A. C. Hutson, A. Sen, (c)J. Am. Chem. Soc, 1991, 113, 700 [Google Scholar]
  31. M. E. Thompson, S. M. Baxter, A. R. Bulls, B. J. Burger, M. C. Nolan, B. D. Santasiero, W. P. Schaefer, J. E. Bercaw, References for tile related “four-centre” electrophilic activation of methane by early transition, lanthanide and actinide metal complexes: (a)J. Am. Chem. Soc, 1987, 109, 203; [Google Scholar]
  32. P. L. Watson, (b)J. Am. Chem. Soc, 1983, 105, 6491; [Google Scholar]
  33. C. M. Fendrick, T. J. Marks, (c)J. Am. Chem. Soc, 1984, 106, 2214 [Google Scholar]
  34. B. R. James, (a)“Homogeneous Hydrogenation”, Wiley, New York, 1977; [Google Scholar]
  35. J. Halpern, (b)Annu. Rev. Phys. Chem., 1965, 16, 103 [Google Scholar]
  36. P. J. Walsh, F. J. Hollander, R. G. Bergman, (a)J. Am. Chem. Soc, 1988, 110, 8729; [Google Scholar]
  37. C. C. Cummins, S. M. Baxter, P. T. Wolczanski, (b)J. Am. Chem. Soc, 1988, 110, 8731 [Google Scholar]
  38. A. Sen, Ace. Chem. Res., 1988, 21, 421 and references therein [Google Scholar]
  39. R. S. Nyholm, Proc. Chem. Soc., 1961, 273 [Google Scholar]
  40. P. M. Henry, D. Reidel, Review: (a)“Palladium Catalyzed Oxidation of Hydrocarbons”, Dordrecht, 1980; [Google Scholar]
  41. R. F. Heck, (b)“Palladium Reagents in Organic Synthesis”, Academic, New York, 1985 [Google Scholar]
  42. Specific examples: (a)op. cit., (Ref. 18); [Google Scholar]
  43. A. Montreux, F. Petit, (b)“Industrial Applications of Homogeneous Catalysis”, Reidel, Dordrecht, 1988; [Google Scholar]
  44. F. J. Waller, (c)J. Mol. Catal., 1985, 31, 123 [Google Scholar]
  45. C. D. Garner, B. Hughes, Review: Adv. In-org. Chem. Radiochem., 1975, 17, 1 [Google Scholar]
  46. A. McKillop, E. C. Taylor, F. G. A. Stone, D. W. Abel, “Comprehensive Organometallic Chemistry”, ed. G. Wilkinson, Pergamon, New York, 1982, Vol. 7, p. 499 [Google Scholar]
  47. M. Trost, P. J. Metzner, J. Am. Chem. Soc, 1980, 102, 3572 [Google Scholar]
  48. G. A. Hamilton, J. R. Giacin, T. M. Hellman, M. E. Snook, J. W. Weller, Ann. N. Y. Acad. Sci., 1973, 212, 4 [Google Scholar]
  49. H. S. Kesling, ACS Symp. Ser., 1987, 328, 77 [Google Scholar]
  50. N. C. Deno, E. J. Jedziniak, L. A. Messer, M. D. Meyer, S. G. Stroud, E. S. Tomezsko, Tetrahedron, 1977, 33, 2503 [Google Scholar]
  51. H. Han, Effect of Lewis acids on arene oxidation by peroxytrifluoroacetic acid: Ace. Chem. Res., 1971, 4, 337 [Google Scholar]
  52. M. N. Vargaftik, I. P. Stolarov, I. I. Moiseev, The oxidation of methane at elevated temperatures (∼180°C) by Co(02CCF3)3 generated in situ has been reported: J. Chem. Soc, Chem. Commun., 1990, 1049. However, this reagent appears to display little activity under the milder conditions that we have employed [Google Scholar]
  53. G. A. Olah, N. Yoneda, D. G. Parker, J. Am. Chem. Soc, 1976, 98, 483, 5261 [Google Scholar]
/content/journals/10.1595/003214091X353126132
Loading
/content/journals/10.1595/003214091X353126132
Loading

Data & Media loading...

  • Article Type: Research Article
This is a required field
Please enter a valid email address
Approval was a Success
Invalid data
An Error Occurred
Approval was partially successful, following selected items could not be processed due to error
Please enter a valid_number test