Synthesis and crystal structure of dimeric dialkylaluminium µ-dialkylamido compounds

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Donald C. Bradley, Ian S. Harding, Izaque A. Maia and Majid Motevalli


Abstract

Dialkylaluminium µ-dialkylamido compounds of formula (R12AlNR22)2 (R1 = Me, Et, Pri, Bui or But; R2 = Me, Et, Pri, Bui or Ph) were synthesized by alkane or arene elimination from the corresponding adduct of formula R13Al·NHR22. The crystal structures of the following dimeric compounds were determined: (Me2AlNEt2)2, (Me2AlNBui2)2, (Et2AlNPri2)2, (Pri2AlNMe2)2, (Pri2AlNEt2)2, (Bui2AlNMe2)2, (Bui2AlNEt2)2 and also the mononuclear compound Et2Al(OEt2)NPh2. The general trends identified in these structures suggest that the environments around aluminium and nitrogen are affected primarily by their closest alkyl groups, i.e. R1 and R2 respectively, but that loss of a centre of symmetry is dependent only on R2. Infrared data can also show the presence of a molecular centre of symmetry. Mass spectroscopic data suggest that dimers are present in the gas phase but they are partially dissociated into monomers which in turn fragment into the more stable species [R1AlNR22]+. The NMR data show that aromatic solvents shield the R2 protons causing downfield chemical shifts. Low-pressure (10-2 Torr) thermal decomposition (500–600 °C) to produce films of aluminium nitride was studied.


References

  1. T. Mole, Organoaluminium Compounds, Elsevier, Amsterdam, 1972, ch. 9, pp. 229–249 Search PubMed.
  2. D. C. Bradley, Adv. Inorg. Chem. Radiochem., 1972, 15, 259 Search PubMed.
  3. M. F. Lappert, P. P. Power, A. R. Sanger and R. C. Srivastava, Metal and Metalloid Amides—Synthesis, Structures and Physical and Chemical Properties, Ellis Horwood, Chichester, 1980, pp. 99–117 and 191–234 Search PubMed.
  4. I. Haiduc and D. B. Sowerby, The Chemistry of Inorganic Homo and Heterocycles, Academic Press, London, 1987, vol. 1, p. 167 Search PubMed.
  5. M. Veith, Adv. Org. Chem., 1990, 31, 269 Search PubMed.
  6. R. G. Gordon, D. M. Hoffman and U. Riaz, J. Mater. Res., 1991, 6, 5 CAS.
  7. R. G. Gordon, U. Riaz and D. M. Hoffman, J. Mater. Res., 1992, 7, 1679 CAS.
  8. Y. Takahashi, K. Yamashita, S. Motojima and K. Sugiyama, Surf. Sci., 1979, 86, 238 CrossRef CAS.
  9. K. L. Ho, K. F. Jensen, J. W. Hwang, W. L. Gladfelter and J. F. Evans, J. Cryst. Growth, 1991, 107, 376 CrossRef CAS.
  10. K. L. Ho, D. C. Boyd, K. F. Jensen, S. A. Hanson, W. L. Gladfelter and J. F. Evans, Mater. Res. Symp. Proc., 1990, 132, 162.
  11. R. K. Schulze, D. R. Mantell, W. L. Gladfelter and J. F. Evans, J. Vac. Sci. Technol. A, 1988, 6, 2162 CrossRef.
  12. D. C. Boyd, R. T. Haasch, D. R. Mantell, R. K. Schulze, J. F. Evans and W. L. Gladfelter, Chem. Mater., 1989, 1, 119 CrossRef CAS.
  13. L. V. Interrante, C. L. Czekaj and Wei Lee, NATO ASI Ser., Ser. B Phys., 1989, 198, 205 Search PubMed.
  14. L. V. Interrante, W. Lee, M. McConnell, N. Lewis and E. Hall, J. Electrochem. Soc., 1989, 136, 472 CAS.
  15. L. V. Interrante, L. E. Carpenter II, C. Whitmarsh and W. Lee, Mater. Res. Soc. Symp. Proc., 1986, 73, 359 CAS.
  16. F. C. Sauls and L. V. Interrante, Coord. Chem. Rev., 1993, 128, 193 CrossRef CAS.
  17. W. L. Gladfelter, D. L. Boyd, J. W. Huang, R. T. Haasch, J. F. Evans, K. L. Ho and K. F. Jensen, Mater. Res. Symp. Proc., 1989, 131, 447 CAS.
  18. D. C. Bradley, M. M. Faktor, D. M. Frigo and E. A. D. White, in Recent Developments in the Preparation and Purification of III–V Precursors, Internal Report, Department of Chemistry, Queen Mary College(currently Queen Mary and Westfield College), London, 1986 Search PubMed.
  19. D. C. Bradley, D. M. Frigo and E. A. D. White, Eur. Pat., EP 0 331 448 A2, 1989 Search PubMed.
  20. I. A. Maia, Ph.D. Thesis, University of London, 1994.
  21. N. Morton, Ph.D. Thesis, University of London, 1993.
  22. M. F. Lappert, P. P. Power, A. R. Sanger and R. C. Srivastava, Metal and Metalloid Amides—Synthesis, Structures and Physical and Chemical Properties, Ellis Horwood, Chichester, 1980, p. 185 Search PubMed.
  23. D. Ya Zhinkin, G. K. Korneeva, N. N. Korneev and M. V. Sobolevskii, J. Gen. Chem. USSR, 1966, 36, 360 Search PubMed.
  24. C. J. Thomas, L. K. Krannich and C. L. Watkins, Polyhedron, 1993, 12, 389 CrossRef CAS.
  25. A. Storr and B. S. Thomas, Can. J. Chem., 1970, 48, 3667 CAS.
  26. O. T. Beachley, G. E. Coates and G. Kohnstam, J. Chem. Soc., 1965, 3248 RSC.
  27. J. Ronayne and D. H. Williams, Annu. Rev. NMR Spectrosc., 1969, 2, 83 Search PubMed.
  28. J. F. Janik, E. N. Duesler and R. T. Paine, Inorg. Chem., 1987, 26, 4341 CrossRef CAS.
  29. A. A. I. Al-Wassil, P. B. Hitchcock, S. Sarisaban, J. D. Smith and C. L. Wilson, J. Chem. Soc., Dalton Trans., 1985, 1929 RSC.
  30. K. M. Waggonner and P. P. Power, J. Am. Chem. Soc., 1991, 113, 3385 CrossRef CAS.
  31. B. Lee, W. T. Pennington and G. H. Robinson, Inorg. Chim. Acta, 1991, 190, 173 CrossRef CAS.
  32. J. J. Byers, B. Lee, W. T. Pennington and G. H. Robinson, Polyhedron, 1992, 11, 967 CrossRef CAS.
  33. D. M. Choquette, M. J. Timm, J. L. Hobbs, M. M. Rahim, K. J. Ahmed and R. P. Planalp, Organometallics, 11, 529 Search PubMed.
  34. S. Amirkalili, P. B. Hitchcock, A. D. Jenkins, J. Z. Nyathi and J. D. Smith, J. Chem. Soc., Dalton Trans., 1981, 377 RSC.
  35. S. J. Schuer, W. T. Pennington and G. H. Robinson, Organometallics, 1992, 11, 3287 CrossRef.
  36. J. J. Byers, W. T. Pennington and G. H. Robinson, Polyhedron, 1990, 9, 2205 CrossRef CAS.
  37. H. Hess, A. Hinderer and S. Steinhauser, Z. Anorg. Allg. Chem., 1970, 377, 1 CrossRef CAS.
  38. L. V. Interrante, G. A. Sigel, M. Garbauskas, C. Hejna and G. A. Slack, Inorg. Chem., 1989, 28, 252 CrossRef CAS.
  39. J. J. Byers, B. Lee, W. T. Pennington and G. H. Robinson, Polyhedron, 1992, 11, 967 CrossRef CAS.
  40. G. M. Sheldrick and W. S. Sheldrick, J. Chem. Soc. A, 1969, 2279 RSC.
  41. M. A. Petrie, K. Ruhlandt-Senge and P. P. Power, Inorg. Chem., 1993, 32, 1135 CrossRef CAS.
  42. G. Socrates, Infrared Characteristic Group Frequencies, Wiley, New York, 1980, p. 54 Search PubMed.
  43. V. G. Schomburg and E. G. Hoffman, Z. Elektrochem., 1957, 61, 1110 Search PubMed.
  44. A. C. Jones and S. A. Rushworth, J. Cryst. Growth, 1990, 106, 253 CrossRef CAS.
  45. A. C. Jones, S. A. Rushworth, D. A. Bohling and G. T. Muhr, J. Cryst. Growth, 1990, 106, 246 CrossRef CAS.
  46. A. C. Jones and S. A. Rushworth, J. Cryst. Growth, 1991, 107, 350 CrossRef CAS.
  47. W. S. Hobson, T. D. Harris, C. R. Abernathy and S. J. Pearton, Appl. Phys. Lett., 1991, 58, 77 CrossRef CAS.
  48. W. L. Gladfelter, D. C. Boyd and K. F. Jensen, Chem. Mater., 1989, 1, 339 CrossRef CAS.
  49. D. B. Beach, S. E. Blum and F. K. LeGoues, J. Vac. Sci. Technol. A, 1989, 3117 CrossRef CAS.
  50. Y. Okuno, H. Asahi, X. F. Liu, K. Inoue, Y. Itani, K. Asami and S. Gonda, J. Cryst. Growth, 1993, 127, 143 CrossRef CAS.
  51. L. H. Dubois, B. R. Zegarski, M. E. Gross and R. G. Nuzzo, Surf. Sci., 1991, 244, 89 CrossRef CAS.
  52. D. C. Bertolet and J. W. Rogers, jun., Chem. Mater., 1993, 5, 391 CrossRef CAS.
  53. M. G. Simmonds, E. C. Phillips, J.-W. Hwang and W. L. Gladfelter, Chemtronics, 1991, 5, 155 Search PubMed.
  54. K. M. Chen, T. Castro, A. Franciosi, W. L. Gladfelter and P. I. Cohen, Appl. Phys. Lett., 1992, 60, 2132 CrossRef CAS.
  55. K. Tsubouchi and K. Masu, J. Vac. Sci. Technol. A, 1992, 10, 856 CrossRef CAS; A. Yamamoto, Organometallic Chemistry, Principle and Applications, Shokabo, Tokyo, 1982, ch. 3 (in Japanese) Search PubMed.
  56. A. C. T. North, D. C. Phillips and F. S. Matthews, Acta Crystallogr., Sect. A, 1968, 24, 351 CrossRef.
  57. G. M. Sheldrick, SHELXS 86, Acta Crystallogr., Sect. A, 1990, 46, 467 CrossRef.
  58. G. M. Sheldrick, SHELXS 80, University of Göttingen, 1980.
  59. G. M. Sheldrick, SHELXL 93, University of Göttingen, 1993.
  60. A. L. Speck, PLATON 96, University of Utrecht, 1996.
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