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Homogeneous Models for Mechanisms of Surface Reactions: Propene Ammoxidation

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Part of the NATO ASI Series book series (ASIC, volume 231)

Abstract

The proposed active sites on the surface of the catalyst for propene ammoxidation have been successfully modeled by structurally characterized pinacolato W(VI) tert-butyl imido complexes. These compounds exist as an equilibrating mixture of amine-bis(imido) and imido-bis(amido) complexes, the position of this equilibrium being dependent on the electronic nature of the glycolate ligand. Both of the C-N bond-forming reactions proposed in recent studies by Kartisek and Grasselli [J. Catal. 81, 489 (1983)] have been reproduced using discrete Group VI d° organoimido complexes under mild conditions suitable for detailed mechanistic studies. These reactions are 1) oxidative trapping of radicals at molybdenum imido sites and 2) migration of the allyl group from oxygen to an imido nitrogen atom.

Keywords

Allylic Alcohol Propargylic Alcohol Propene Ammoxidation Homogeneous Analogue Imido Group 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.

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References

  1. 1.
    D.M.T. Chan, W.C. Fultz, W.A. Nugent, D.C. Roe, and T.H. Tulip, J. Am. Chem. Soc. 107, 251 (1985).CrossRefGoogle Scholar
  2. 2.
    D.M.T. Chan and W.A. Nugent, Inorg. Chem. 24, 1422 (1985).CrossRefGoogle Scholar
  3. 3.
    For reviews on the mechanism of propene ammoxidation see:Google Scholar
  4. 3. (a)
    a.G.W. Keulks, L.D. Krenzke, and T.M. Notermann, Adv. Catal. 27, 183 (1978).CrossRefGoogle Scholar
  5. 3. (b)
    b.J. Haber and A. Bielanski, Catal. Rev. Sci. Eng. 19, 1 (1979).Google Scholar
  6. 3. (c)
    c.B.C. Gates, J.R. Katzer, and G.C.A. Schuit, Chemistry of Catalytic Processes, pp.325–389, McGraw-Hill, New York, (1979).Google Scholar
  7. 3. (d)
    d.J.D. Burrington, C.T. Kartisek, and R.K. Grasselli, J. Catal. 81, 489 (1983).CrossRefGoogle Scholar
  8. 4.
    W. Martir and J.H. Lunsford, J. Am. Chem. Soc. 1103, 3728 (1981).CrossRefGoogle Scholar
  9. 5.
    J.D. Burrington, C.T. Kartisek, and R.K. Grasselli, J. Catal. 87, 363 (1984).CrossRefGoogle Scholar
  10. 6.
    However, oxidation of radicals with C-0 bond formation to ligand oxygen atom is known:Google Scholar
  11. J.K. Kochi, J. Org. Chem. 30, 1862 (1965).CrossRefGoogle Scholar
  12. F. Gaudemer and A. Gaudemer, Tetrahedron Lett. 21, 1445 (1980).CrossRefGoogle Scholar
  13. Rate constants for oxidation of alkyl radicals by permanganate are close to the diffusion-controlled limit:Google Scholar
  14. S. Streenken and P. Neta, J. Am. Chem. Soc. 104, 1244 (1982).CrossRefGoogle Scholar
  15. 7.
    An analogy can be made between 0 to N migration and the rearrangement of allylic and propargylic alcohols promoted by d° vanadium and tungsten oxo complexes:Google Scholar
  16. T. Hosogai, Y. Fujita, Y. Ninagawa, and T. Nishida, Chem. Lett. 357 (1982), and references cited therein.Google Scholar
  17. See also: B.J. Kane, U.S. Patent 4,254,291 (1981).Google Scholar
  18. 8.
    W.A. Nugent, Inorg. Chem. 22, 965 (1983).CrossRefGoogle Scholar
  19. 9.
    W.A. Nugent and R.L. Harlow, Inorg. Chem. 19, 1977 (1980).CrossRefGoogle Scholar
  20. 10. (a)
    W.J. Middleton and R.V. Lindsey, J. Am. Chem. Soc. 86, 4948 (1964).CrossRefGoogle Scholar
  21. 10. (b)
    (b)G.W. Astrologen and J.C. Martin, J. Am. Chem. Soc. 98, 2895 (1976).CrossRefGoogle Scholar
  22. 11.
    Spectroscopic assignments were based on other imido complexes; see ref. 9 and W.A. Nugent, R.L. Minney, R.V. Kasowski, and F.A. Van Catledge, Inorg. Chim. Acta 65, L91 (1982). The ratios of isomers 4 and 5 are determined by spectral integration of the NMR t-Bu signals.Google Scholar
  23. 12.
    Compare: S.M. Rocklage, R.R. Schrock, M.R. Churchill, and H.J. Wasserman, Organometallics 1, 1332 (1982).CrossRefGoogle Scholar
  24. 13.
    Y. Iwasawa, T. Nakamura, K. Takamatsu, and S.J. Ogasawara, J. Chem. Soc., Faraday Trans. 1 76, 939 (1980).Google Scholar
  25. See also: A.K. Rappe and W.A. Goddard III, J. Am. Chem. Soc. 104, 3827 (1982).CrossRefGoogle Scholar
  26. 14.
    In fact, methylbenzenes, under ammoxidation conditions, are converted to the corresponding benzonitriles in high yield:Google Scholar
  27. R.A. Sheldon and J.K. Kochi, in Metal-Catalyzed Oxidations of Organic Compounds, pp. 324–325, Academic Press, New York (1981).Google Scholar
  28. 15.
    The observation that the yield of the organic imine product never exceeded 50% based on metal suggests the possibility that the last step in the product formation is a bimolecular process requiring a second equivalent of metal oxidant.Google Scholar
  29. 16.
    J.D. Burrington, C.T. Kartisek, and R.K. Grasselli, J. Catal. 63, 235 (1980).CrossRefGoogle Scholar

Copyright information

© Kluwer Academic Publishers 1988

Authors and Affiliations

  1. 1.Central Research and Development Department, Experimental StationE. I. du Pont de Nemours & Co.WilmingtonUSA

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