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Heterometal Alkoxides as Precursors in the Sol-Gel Process

  • Ram C. Mehrotra
Chapter

Abstract

The preparation of a series of bimetallic alkoxides during the last three decades has been followed by a successful synthesis of intriguingly stable heterometal alkoxides containing three or four different metal atoms in the same molecular species during the past five years.

The increasing importance of the use of mixtures of a number of metal alkoxides as precursors for the preparation of a wide variety of novel ceramics by the SOLUTION-SOL-GEL (S-S-G) process has led to the possibility of molecularly designing a single source precursor suited to the composition of the targeted final ceramic. This has been made feasible by the extraordinary stability of the framework of heterometal alkoxides, which appears to remain intact during the initial hydrolysis reactions in the S-S-G process.

The characterization (by sophisticated physicochemical techniques including X-Ray crystal structure determination in some cases) of these heterometal alkoxides has added a new class of heterometal coordination systems which are found to be uniquely stable without the presence of metal-metal bonds or auxiliary ligands like CO, etc., generally required for stabilizing polymetallic systems known so far. A clearer understanding of their structural features is providing not only a valuable insight into the mechanism of their reactivity in the S-G process, but is resulting in refinements which enhance the capabilities of the procedures for the synthesis of more and more novel materials.

Keywords

Metal Alkoxide Bivalent Metal Aluminium Isopropoxide Auxiliary Ligand Single Source Precursor 
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.
    H. Meerwein and T. Bersin, Ann. 476: 113 (1929).Google Scholar
  2. 2.
    R.C. Mehrotra and A. Mehrotra, Inorg. Chim. Acta Rev. 5: 127 (1971).CrossRefGoogle Scholar
  3. 3.
    W.G. Bartley and W. Wardlaw, J. Chem. Soc. 421 (1958).Google Scholar
  4. 4.
    D.C. Bradley, R.C. Mehrotra and D.P. Gaur, Metal Alkoxides, Academic Press, London (1978).Google Scholar
  5. 5.
    R.C. Mehrotra, in: Advances in Inorganic Chemistry and Radiochemistry A.G. Sharpe and H.J. Emeleus, ed., Academic Press, New York (1983) Vol. 26, page 269.Google Scholar
  6. 6.
    R.C. Mehrotra and M. Aggarwal, Polyhedron 4: 845 (1985).CrossRefGoogle Scholar
  7. 7.
    R.K. Dubey, A. Singh and R.C. Mehrotra, J. Organometal Chem. (Eaborn Issue) 341: 569 (1988).CrossRefGoogle Scholar
  8. 8.
    R.K. Dubey, A. Shah, A. Singh and R.C. Mehrotra, Recuil (Van der Kirk Issue) 107: 237 (1988).Google Scholar
  9. 9.
    R.C. Mehrotra, J. Non-Cryst. Solids 100: 1 (1988).CrossRefGoogle Scholar
  10. 10.
    H. Dislich, Angew. Chemie (Int. Ed.) 10: 363 (1971).CrossRefGoogle Scholar
  11. 11.
    R.C. Mehrotra, Mat. Res. Soc. Symp. Proc. 121: 81 (1988).CrossRefGoogle Scholar
  12. 12.
    R.C. Mehrotra in: Sol-Gel-Science and Technology: M.A. Aegerter, M. Jaffelicci Jr., D.F. Souza and E.D. Zanotto, ed., World Scientific, Singapore (1989) p. 24.Google Scholar
  13. 13.
    D.C. Bradley, Chem. Rev. 89: 1317 (1989).CrossRefGoogle Scholar
  14. 14.
    K.G. Caulton and L.G. Pfalzgraf, Chem. Rev. 90: 969 (1990).CrossRefGoogle Scholar
  15. 15.
    R.C. Mehrotra, Chemtracts 2: 389 (1990).Google Scholar
  16. 16.
    R.C. Mehrotra, J. Organomet. Chem. (Russian) 3 729 (1990).Google Scholar
  17. 17.
    R.C. Mehrotra, A. Singh and U.M. Tripathi, Chem. Rev. 91: 1287 (1991).CrossRefGoogle Scholar
  18. 18.
    R.C. Mehrotra, Nat. Acad. Sc. Letters 14: 153 (1991).Google Scholar
  19. 19.
    R.C. Mehrotra, Ind. J. Chem. 31A: 492 (1992).Google Scholar
  20. 20.
    P.N. Kapoor and R.C. Mehrotra, Coord. Chem. Rev. 14 1 (1974).CrossRefGoogle Scholar
  21. 21.
    R.C. Mehrotra, Proc. Ind. Nat. Sc. Acad. 42: 1 (1976).Google Scholar
  22. 22.
    R.C. Mehrotra, Kemiai Kozlemenyck 45: 197 (1975).Google Scholar
  23. 23.
    W.J. Evans, T.J. Deming, J.M. Olofson and J.W. Ziller, Inorg. Chem. 28: 4027 (1989).CrossRefGoogle Scholar
  24. 24.
    F.A. Cotton, D.O. Marier and W. Schevotzer, Inorg. Chem. 25: 4211 (1984).CrossRefGoogle Scholar
  25. 25.
    R.G. Jones, E.B. Bindschadler, D. Blume, G. Karmas, G.A. Marten, J.R. Thirtle and H. Gilman, J. Am. Chem. Soc. 78 6027 (1956).CrossRefGoogle Scholar
  26. 26.
    R.C. Mehrotra, J.M. Batwara and P.N. Kapoor, Coord. Chem. Rev. 31: 67 (1980).CrossRefGoogle Scholar
  27. 27.
    N. Ya Tuvova, V.A. Kozunov, A.L. Yanovashii, N.G. Bokil, Yu. T. Struchkor and B.L. Tamopolskii, J. Inorg. Nucl. Chem. 41: 5 (1979).CrossRefGoogle Scholar
  28. 28.
    L.M. Brown and K.S. Mazdiyasni, Inorg. Chem. 9: 2783 (1970).CrossRefGoogle Scholar
  29. 29.
    O. Poncelet, W.J. Sartain, L.G. Pfalzgraf, K. Folting, and K.G. Caulton, Inorg. Chem. 28: 263 (1989).CrossRefGoogle Scholar
  30. 30.
    R.C. Mehrotra, Chemtracts 2: 143 (1990).Google Scholar
  31. 31.
    J.G. Reiss and L.G. Pfalzgraf, Bull. Soc. Chim. France 2401: 4348 (1968).Google Scholar
  32. 32.
    R.C. Mehrotra, R. Jain and A.K. Rai, J. Inorg. Chem. (China) 3: 96 (1987).Google Scholar
  33. 33.
    S. Govil, P.N. Kapoor and R.C. Mehrotra, Inorg. Chim. Acta 15: 43 (1975).CrossRefGoogle Scholar
  34. 34.
    R.K. Dubey, A. Singh and R.C. Mehrotra, Inorg. Chim. Acta 118: 151 (1986).CrossRefGoogle Scholar
  35. 35.
    R. Jain, A.K. Rai and R.C. Mehrotra, Z. Naturfors. 40b: 1371 (1985).Google Scholar
  36. 36.
    R.C. Mehrotra, M. Aggrawal and C.K. Sharma, Synth. React. Inorg. Met. Org. Chem. 13: 571 (1984).Google Scholar
  37. 37.
    R.K. Dubey, A. Singh and R.C. Mehrotra, Inorg. Chim. Acta. 143: 169 (1988).CrossRefGoogle Scholar
  38. 38.
    A. Shah, A. Singh and R.C. Mehrotra, Ind. J. Chem. 27A: 372 (1988).Google Scholar
  39. 39.
    R.C. Chhipa, A. Singh and R.C. Mehrotra, Synth. React. Inorg. Met-Org. Chem. 20: 989 (1990).CrossRefGoogle Scholar
  40. 40.
    U.M. Tripathi, A. Singh and R.C. Mehrotra, Polyhedron 10: 949 (1991).CrossRefGoogle Scholar
  41. 41.
    D.C. Bradley, Phil Trans. Roy. Soc. London A330:167 (1990).Google Scholar
  42. 42.
    S. Sogani, R. Bohra. M. Nattemeyer, A. Singh and R.C. Mehrotra, J. Chem. Soc. Chem. Commn. 738 (1991).Google Scholar
  43. 43.
    U.M. Tripathi, A. Singh, R.C. Mehrotra, S.C. Geel, M.Y. Chiang and W.E. Buhro, J. Chem. Soc. Chem. Commn. 152 (1992).Google Scholar
  44. 44.
    R.C. Mehrotra, J. Ind. Chem. Soc. 30: 585 (1953).Google Scholar
  45. 45.
    M. Aggrawal and R.C. Mehrotra, Polyhedron 4:1141 (1985).CrossRefGoogle Scholar
  46. 46.
    U.M. Tripathi, A. Singh and R.C. Mehrotra, Polyhedron 10: 949 (1991).CrossRefGoogle Scholar
  47. 47.
    U.M. Tripathi, Ph.D. Thesis, University of Rajasthan, Jaipur (1992).Google Scholar
  48. 48.
    S. Sogani, A. Singh and R.C. Mehrotra, Main Group Metal Chem. 15: 197 (1992); Ind. J. Chem. 32A: 345 (1993).Google Scholar
  49. 49.
    S. Sogani, Ph.D. Thesis University of Rajasthan, Jaipur (1992).Google Scholar
  50. 50.
    S. Mathur, A. Singh and R.C. Mehrotra, Polyhedron 11: 341 (1992).CrossRefGoogle Scholar
  51. 51.
    S. Mathur, Ph.D. Thesis University of Rajasthan, Jaipur (1992).Google Scholar
  52. 52.
    R.K. Dubey, A. Singh and R.C. Mehrotra, Ind. J. Chem. 31A: 156 (1992).Google Scholar
  53. 53.
    R. Gupta, A. Singh and R.C. Mehrotra, Ind. J. Chem. 30A: 592 (1991).Google Scholar
  54. 54.
    R. Gupta, A. Singh and R.C. Mehrotra, New J. Chem. 15: 665 (1991); Ind. J. Chem. 32A: 310 (1993).Google Scholar
  55. 55.
    G. Garg, A. Singh and R.C. Mehrotra, Ind. J. Chem. 30A: 688, 866 (1991); Synth. React. Inorg. Met-Org. Chem. 21: 1047 (1991).Google Scholar
  56. 56.
    G. Garg, R.K. Dubey, A. Singh and R.C. Mehrotra, Polyhedron 10: 1733 (1991).CrossRefGoogle Scholar
  57. 57.
    R.C. Chhipa, A. Singh and R.C. Mehrotra, Synth. React. Inorg. Met-Org. Chem. 20: 989 (1990); Ind. J. Chem. 30A: 1024 (1991).Google Scholar
  58. 58.
    R.C. Mehrotra and J.V. Singh, Can. J. Chem. 62: 1003 (1984).CrossRefGoogle Scholar
  59. 59.
    R.C. Mehrotra, M.M. Agrawal and P.N. Kapoor, J. Chem. Soc. 1203 (1968).Google Scholar
  60. 60.
    R.C. Mehrotra and J.V. Singh, Z. Anorg. Allgem. Chem. 522: 211 (1984).Google Scholar
  61. 61.
    S. Govil, P.N. Kapoor and R.C. Mehrotra, J. Inorg. Nucl. Chem. 38: 172 (1976).CrossRefGoogle Scholar
  62. 62.
    J. Rai, Ph.D. Thesis, University of Rajasthan, Jaipur (1992).Google Scholar
  63. 63.
    S. Hirano, T. Hayashi, K. Nosaki and K. Kato, J. Am. Ceram. Soc. 72: 707 (1989).CrossRefGoogle Scholar
  64. 64.
    S. Hirano and K. Kato, Bull. Chem. Soc. Jpn. 62: 429 (1989); Solid State Ionics 32/33: 765 (1989).CrossRefGoogle Scholar
  65. 65.
    F. Chaput, J. Boilot, M. Lejeune, R. Papiernik and L.G. Hubert-Pfalzgraf, J. Am. Ceram. Soc. 72: 1335 (1989).CrossRefGoogle Scholar
  66. 66.
    R. Papiernik, L.G. Hubert-Pfalzgraf, A.M. Massiani, F. Chaput, J.P. Boilot, 0. Bouquin and Lejeune, Am. Chem. Soc. Meeting, Los. Angeles (1988), Paper No. Inorg. 230.Google Scholar
  67. 67.
    R.C. Mehrotra, J. Non-Cryst. Solids 145: 1 (1992).CrossRefGoogle Scholar
  68. 68.
    R.C. Mehrotra, M.M. Agrawal and P.N. Kapoor, J. Chem. Soc. (A): 2673 (1968).Google Scholar
  69. 69.
    A. Nazeri-Eshighi, A.X. Kuang and J.D. Mackenzie, J. Mat. Sc 25: 3333 (1990).CrossRefGoogle Scholar
  70. 70.
    S.C. Goel, K.S. Kramer, P.C. Gibbons and W.E. Buhro, Inorg. Chem 28: 1619 (1989).CrossRefGoogle Scholar
  71. 71.
    G. Kordas, J. Non-Cryst. Solids 121: 436 (1990).CrossRefGoogle Scholar
  72. 72.
    N.N. Sauer, E. Gracia, K.V. Salazar, R.R. Ryan and J.A. Marten, J. Am. Chem. Soc 121: 1524 (1990).CrossRefGoogle Scholar
  73. 73.
    S. Sakka, J. Non-Cryst. Solids 121: 417 (1990).CrossRefGoogle Scholar
  74. 74.
    A.H. Cowley and R.A. Jones, Angew. Chem. (Int. Ed.) 28: 1208 (1992).CrossRefGoogle Scholar
  75. 75.
    L.L. Hench and J.K. West, Chem. Rev 90: 33 (1990).CrossRefGoogle Scholar
  76. 76.
    J. Rai and R.C. Mehrotra, J. Non-Cryst. Solids 152: 118 (1993).CrossRefGoogle Scholar
  77. 77.
    Jai Rai and R.C. Mehrotra, Main Group Metal Chem. 15: 209 (1992).Google Scholar
  78. 78.
    R. Kuhlman, B.A. Vaaristra, W.E. Streib, J.C. Huffman, K.G. CulatonInorg. Chem 32: 1272 (1993).CrossRefGoogle Scholar
  79. 79.
    M.J. Hampden-Smith, D.S. Williams and A.L. Rheingold, Inorg. Chem 29: 4076 (1990).CrossRefGoogle Scholar
  80. 80.
    B.A. Vaarstra, J.C. Huffman, W.E. Streib and K.G. Caulton, 30: 3068 (1991).Google Scholar
  81. 81.
    R.C. Mehrotra, in ‘Chemistry and Technology of Silicon and Tin’, ed., V.G. Kumar Das, N. Seik Weng and M. Gielen (Oxford Univ. Press, 1991) pp. 93–109.Google Scholar
  82. 82.
    I.M. Thomas, in ‘Sol-Gel Technology for Thin Films, Fibres, Preforms, Electronics and Speciality Shapes’, ed. Klein (Noyes, N. Jersey, 1988) p. 7.Google Scholar
  83. 83.
    J. Rai and R.C. Mehrotra, J. Non-Cryst. Solids 134: 23 (1991).CrossRefGoogle Scholar
  84. 84.
    R. Papiernik, L.G. Hubert-Pfalzgraf, J. Doran and Y. Jeannin, J. Chem. Soc. Chem. Commn.: 696 (1990).Google Scholar
  85. 85.
    J. Campion, D.A. Payne, H.K. Chae, J.K. Mausin and S.R. Wilson, Inorg. Chem 30: 3245 (1991).CrossRefGoogle Scholar
  86. 86.
    U. Bemrn, R. Norrestam, M. Nygren and G. Westen, Inorg. Chem 31: 2050 (1992).CrossRefGoogle Scholar
  87. 87.
    S.C. Goel, M.Y. Chiang, P.C. Gibbons and W.E. Buhro, Mat. Res. Soc. Symp. Proc. 271: 3 (1992).CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media New York 1994

Authors and Affiliations

  • Ram C. Mehrotra
    • 1
    • 2
  1. 1.University of AllahabadAllahabadIndia
  2. 2.Chemical LaboratoriesUniversity of RajasthanJaipurIndia

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