Mixed Si/C/M/O ceramics from 2,5-disilahexane/metal carbonyl (M[double bond, length as m-dash]Fe and Co)

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Stéphane Bourg, Bruno Boury and Robert J. P. Corriu


Abstract

Reactions of 2,5-disilahexane with cobalt or iron carbonyl were performed in order to prepare cobalt or iron organosilicon ceramic precursors. Characterization of their structure by NMR and IR spectroscopies indicates the presence of mixed oligomeric and molecular species. Pyrolysis under argon at 1000 °C gives multiphase ceramics in high yields. Part of the CO ligands were incorporated during the thermal decomposition. Materials were characterized by X-ray, Raman, TEM and magnetic susceptibility analyses. For cobalt and iron, formation of metal-rich nodules included in a homogeneous matrix is observed for the sample pyrolyzed at 1000 °C. Crystalline Fe3Si or Co2Si are detected and the presence of amorphous oxide or oxycarbide phases is consistent with the high oxygen level. Between 1200 °C and 1400 °C, a carbothermal reduction process occurs at different temperatures for the iron and the cobalt precursors. Elimination of CO and SiO occurs with modification of the ceramic phases. Formation of SiC and silicides (FeSi for I and CoSi for II) is observed. Melting of the Fe3Si phase leads to the formation of spherical metallic particles.


References

  1. M. Birot, J. P. Pillot and J. Dunoguès, Chem. Rev., 1995, 95, 1443 CrossRef CAS.
  2. D. Seyferth, H. Lang, C. A. Sobon, J. Borm, H. J. Tracy and N. Bryson, J. Inorg. Org. Polym., 1992, 2, 59 Search PubMed.
  3. D. Seyferth and G. H. Wieseman, J. Am. Ceram. Soc., 1984, 67, C.
  4. S. Yajima, J. Hayashi and M. Omori, Chem. Lett., 1975, 931 CAS.
  5. K. Thorne, E. Liimatta and J. D. Mackenzie, J. Mater. Res., 1991, 6, 2199 CAS.
  6. D. Seyferth, in Silicon based polymer science. A comprehensive resource, ed. J. M. Ziegler and F. W. G. Fearon, American Chemical Society, Washington, DC, 1990, ch. 31 Search PubMed.
  7. C. L. Schilling, J. P. Wesson and T. C. Williams, Am. Ceram. Soc. Bull., 1983, 62, 912 CAS.
  8. C. L. Czekaj, M. L. Hackney, W. J. Hurley, L. V. Interrante and G. A. Siegel, J. Am. Ceram. Soc., 1990, 73, 352 CAS.
  9. R. J. P. Corriu, P. Gerbier, C. Guerin and B. Henner, Angew. Chem., Int. Ed. Engl., 1992, 31, 1195 CrossRef.
  10. R. J. P. Corriu, P. Gerbier, C. Guerin and B. Henner, in Silicon-Containing Polymers, ed. R. G. Jones, Royal Society of Chemistry, Cambridge, 1995, p. 3 Search PubMed.
  11. R. J. P. Corriu, P. Gerbier, C. Guerin and B. Henner, in Applications of the Organometallic Chemistry in the Preparation and Processing of Advanced Materials, ed. F. H. Harrod and R. M. Laine, Kluwer Academic, London, 1995, p. 203 Search PubMed.
  12. B. J. Aylett and H. M. Colquhoun, J. Chem. Soc., Dalton Trans., 1977, 2058 RSC.
  13. B. Z. Tang, R. Petersen, D. A. Foucher, A. Lough, N. Coombs, R. Sodhi and I. Manners, J. Chem. Soc., Chem. Commun., 1993, 523 RSC.
  14. R. J. P. Corriu, N. Devylder, C. Guerin, B. Henner and A. Jean, J. Organomet. Chem., 1996, 509, 249 CrossRef CAS.
  15. B. Boury, R. J. P. Corriu and L. Carpenter, Angew. Chem., Int. Ed. Engl., 1990, 29, 785 CrossRef.
  16. S. Huille, Thèse de l'Université Montpellier II, 1993.
  17. L. Lutsen, Thèse de l'Université Montpellier II, 1994.
  18. R. J. P. Corriu, M. Enders, S. Huille, L. Lutsen and J. E. Moreau, in Applications of the Organometallic Chemistry in the Preparation and Processing of Advanced Materials, ed. F. H. Harrod and R. M. Laine, Kluwer Academic, London, 1995, p. 185 Search PubMed.
  19. T. D. Tilley, in The Silicon Heteroatom Bond, ed. S. Patai and Z. Rappoport, Wiley, New York, 1991, p. 245 Search PubMed.
  20. G. Bellachioma, G. Cardaci, E. Colomer, R. J. P. Corriu and A. Vioux, Inorg. Chem., 1989, 28, 519 CrossRef CAS.
  21. L. Vancea and W. A. G. Graham, Inorg. Chem., 1974, 13, 511 CrossRef CAS.
  22. C. P. S. Bhanu, R. J. P. Corriu and G. Lanneau, Organometallics, 1995, 14, 1657 CrossRef CAS.
  23. D. S. Knight and W. B. White, J. Mater. Res., 1989, 4, 385 CrossRef CAS.
  24. U. Schubert, J. Müller and H. G. Alt, Organometallics, 1987, 6, 469 CrossRef CAS.
  25. M. Cowie and M. J. Bennett, Inorg. Chem, 1977, 16, 2321 CrossRef CAS.
  26. E. Colomer, R. J. P. Corriu, C. Marzin and A. Vioux, Inorg. Chem., 1982, 21, 369.
  27. M. J. Bennett and K. A. Simpson, J. Am. Chem. Soc., 1971, 93, 7156 CrossRef CAS.
  28. M. E. Schlesinger, Chem. Rev., 1990, 90, 607 CrossRef CAS.
  29. R. J. P. Corriu, S. Huille and J. J. E. Moreau, Chem. Mater., 1994, 15, 6.
  30. J. P. Collman, L. S. Hegedus and R. G. Norton, in Principles and Applications of Organotransition Metal Chemistry, Mill Valley, CA, 1987 Search PubMed.
  31. R. B. King, Adv. Organomet. Chem., 1964, 2, 157 CAS.
  32. T. C. Chou and J. Wadsworth, J. Mater. Res., 1991, 6, 796 CAS.
  33. Y. Pan and J. L. Baptista, J. Am. Ceram. Soc., 1996, 79, 2017 CAS.
  34. N. Klinger, E. L. Strauss and K. L. Komarek, J. Am. Ceram. Soc., 1966, 49, 369 CAS.
  35. J. J. Biernacki and J. Wotzak, J. Am. Ceram. Soc., 1989, 72, 122 CAS.
  36. S. Bourg, B. Boury, F. Carre and R. J. P. Corriu, Organometallics, 1997, 16, 3097 CrossRef.