Advertisement

Large Molecular Metal Carbonyl Clusters: Models of Metal Particles

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

Abstract

The structures of large molecular metal carbonyl clusters often may be described as fragments of metal lattices stabilized by carbonyl ligands; these structures do not support the common belief that growth of metal aggregates occurs via icosahedral packing. Only a few examples of clusters possessing fivefold symmetry are known. It may be argued that ligands play a role in determining the cluster geometries. A similarity in magnetic behaviour of metal carbonyl clusters and metal crystallites is emerging, which seems to substantiate theoretical predictions of a transition from Pauli- to Curie-type behaviour on going from bulk to particulate metals. Interstitial carbide clusters also show bulk structural behaviour; however, the higher degree of freedom of molecular entities is often reflected in their unusual geometries, which may probably be related to those of carbidized metal particles. The reactions of carbide clusters, either with CO + H2 or acids, give rise to stoichiometric formation of hydrocarbons; these reactions bear some formal resemblance to Fischer-Tropsch synthesis.

Keywords

Metal Frame Pentagonal Bipyramid Carbonyl Cluster Small Metal Particle Metal Crystallite 
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.

Preview

Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.

References

  1. 1.
    J.R. Anderson, Structure of Metallic Catalysts, Academic Press, London and New York (1975).Google Scholar
  2. 2.
    S.C. Davis and K.J. Klabunde, Chem. Rev. 82, 153 (1982).CrossRefGoogle Scholar
  3. 3.
    J.J. Burton, Catal. Rev. 9, 209 (1974).CrossRefGoogle Scholar
  4. 4.
    J. Koutecky and P. Fantucci, Chem. Rev. 86, 539 (1986).CrossRefGoogle Scholar
  5. 5.
    J.C. Phillips, Chem. Rev. 86, 619 (1986).CrossRefGoogle Scholar
  6. 6.
    B.F.G. Johnson, Transition Metal Clusters, J. Wiley and Sons, New York (1980).Google Scholar
  7. 7.
    M. Moskovits, Acc. Chem. Res. 12, 229 (1979).CrossRefGoogle Scholar
  8. 8.
    J.M. Basset and R. Ugo, Aspects of Homogeneous Catalysis, (Ed. R. Ugo), v. 3, p. 137, Reidel, Dordrecht and Boston (1977).Google Scholar
  9. 9.
    E.L. Muetterties and M.J. Krause, Angew. Chem., Int. Ed. Engl. 22, 135 (1983).CrossRefGoogle Scholar
  10. 10.
    P. Chini, Gazz. Chim. Ital. 109, 225 (1979).Google Scholar
  11. 11.
    P. Chini, J. Organomet. Chem. 200, 37 (1980).CrossRefGoogle Scholar
  12. 12.
    E.L. Muetterties and J. Stein, Chem. Rev. 79, 479 (1979).CrossRefGoogle Scholar
  13. 13.
    R. Ugo and R. Psaro, J. Mol. Catal. 20, 53 (1983).CrossRefGoogle Scholar
  14. 14.
    R.D. Adams and I.T. Horvath, Prog. Inorg. Chem. 33, 127 (1985).CrossRefGoogle Scholar
  15. 15.
    R.C. Baetzold, Inorg. Chem. 20, 118 (1981).CrossRefGoogle Scholar
  16. 16.
    G. Ciani, A. Sironi, and S. Martinengo, J. Chem. Soc., Dalton Trans., 519 (1981).Google Scholar
  17. 17.
    V.G. Albano, G. Ciani, S. Martinengo, and A. Sironi, J. Chem. Soc., Dalton Trans., 978 (1979).Google Scholar
  18. 18.
    V.G. Albano, A. Ceriotti, P. Chini, G. Ciani, S. Martinengo, and W.M. Anker, J. Chem. Soc., Chem. Commun., 860 (1975).Google Scholar
  19. 19.
    A. Fumagalli, S. Martinengo, and G. Ciani, J. Chem. Soc., Chem. Commun., 1381 (1983).Google Scholar
  20. 20.
    S. Martinengo, G. Ciani, and A. Sironi, J. Chem. Soc., Chem. Commun., 1140 (1980).Google Scholar
  21. 21.
    S. Martinengo, G. Ciani, A. Sironi, and P. Chini, J. Am. Chem. Soc. 100, 7097 (1978).CrossRefGoogle Scholar
  22. 22.
    J.L. Vidal and R.C. Schoening, Inorg. Chem. 20, 265 (1981).CrossRefGoogle Scholar
  23. 23.
    G. Ciani, A. Sironi, and S. Martinengo, J. Organomet. Chem. 192, C42 (1980).CrossRefGoogle Scholar
  24. 24.
    A. Fumagalli, S. Martinengo, G. Ciani, and A. Sironi, XVI Cong. Naz. Chim. Inorg., Ferrara, 402 (1983).Google Scholar
  25. 25.
    J.L. Vidal, L.A. Kapicak, and J.M. Troup, J. Organomet. Chem. 215, C11 (1981).CrossRefGoogle Scholar
  26. 26.
    G. Ciani, A. Magni, A. Sironi, and S. Martinengo, J. Chem. Soc., Chem. Commun., 1280 (1981).Google Scholar
  27. 27.
    S. Martinengo, G. Ciani, and A. Sironi, J. Am. Chem. Soc. 102, 7564 (1980).CrossRefGoogle Scholar
  28. 28.
    J.L. Vidal, R.C. Schoening, and J.M. Troup, Inorg. Chem. 20, 227 (1981).CrossRefGoogle Scholar
  29. 29.
    A. Fumagalli, S. Martinengo, G. Ciani, N. Masciocchi, and A. Sironi, XVIII Cong. Naz. Chim. Inorg., Como, 148 (1985).Google Scholar
  30. 30.
    E.G. Mednikov, N.K. Eremenko, Yu.L. Slovokhotov, and Yu.T. Struchov, J. Organomet. Chem. 301, C35 (1986).CrossRefGoogle Scholar
  31. A. Ceriotti, P. Chini, G. Longoni, D.M. Waschecheck, E.J. Wucherer, L.F. Dahl, M. Marchionna, and R.A. Montag, unpublished results.Google Scholar
  32. 32.
    A. Ceriotti, F. Demartin, G. Longoni, M. Manassero, M. Marchionna, G. Piva, and M. Sansoni, Angew. Chem., Int. Ed. Engl. 24, 696 (1985).CrossRefGoogle Scholar
  33. 33.
    A.F. Wells, Structural Inorganic Chemistry, IVth, Clarendon Press, Oxford (1975).Google Scholar
  34. 34.
    G. Ciani and A. Sironi, J. Organomet. Chem. 197, 233 (1980).CrossRefGoogle Scholar
  35. 35.
    G. Longoni, M. Manassero, and M. Sansoni, J. Am. Chem. Soc. 102, 7973 (1980).CrossRefGoogle Scholar
  36. 36.
    A. Ceriotti, F. Demartin, G. Longoni, M. Manassero, G. Piva, G. Piro, M. Sansoni, and B.T. Heaton, J. Organomet. Chem. 301, C5 (1986).CrossRefGoogle Scholar
  37. A. Ceriotti, P. Ingallina, G. Longoni, M. Marchionna, F. Demartin, and M. Manassero, unpublished results.Google Scholar
  38. 38.
    J.H. Sinfelt, Acc. Chem. Res. 10, 15 (1977).CrossRefGoogle Scholar
  39. 39.
    W.M.H. Sachtler and R.A. Van Santen, Adv. Catal. 26, 169 (1977).Google Scholar
  40. 40.
    W.M.H. Sachtler, Vide 164, 67 (1973).Google Scholar
  41. 41.
    B.K. Teo and N.J.A. Sloane, Inorg. Chem. 24, 4545 (1985).CrossRefGoogle Scholar
  42. 42.
    A.J. Melmed and D.O. Hayward, J. Chem. Phys. 31, 545 (1959).CrossRefGoogle Scholar
  43. 43.
    F. Ogburn, B. Paretzkin, and H.S. Peiser, Acta Crystallogr. 17, 774 (1964).CrossRefGoogle Scholar
  44. 44.
    M.A. Gedwill, G.J. Alstetter, and C.M. Weyman, J. Appl. Phys. 35, 2266 (1964).CrossRefGoogle Scholar
  45. 45.
    R.L. Schwoebel, J. Appl. Phys. 37, 2515 (1966).CrossRefGoogle Scholar
  46. 46.
    R.W. De Blois, J. Appl. Phys. 36, 1647 (1965).CrossRefGoogle Scholar
  47. 47.
    G.L. Downs and J.D. Braun, Science 154, 1443 (1966).CrossRefGoogle Scholar
  48. 48.
    S. Ino, J. Phys. Soc. Japan 21, 346 (1966).CrossRefGoogle Scholar
  49. 49.
    A. Renou and M. Gillet, Surf. Sci. 106, 27 (1981).CrossRefGoogle Scholar
  50. 50.
    D. Schechtman, I.Blech, D. Gratias, and J.W. Cahn, Phys. Rev. Lett. 53, 1951 (1984).CrossRefGoogle Scholar
  51. 51.
    H.W. Kroto, J.R. Heath, S.C. Orien, R.F. Curl, and R.E. Smally, Nature (London) 318, 162 (1985).CrossRefGoogle Scholar
  52. 52.
    A.D.J. Haymet, J. Am. Chem. Soc. 108, 319 (1986).CrossRefGoogle Scholar
  53. 53.
    B. Bagley, Nature (London) 225, 1040 (1970).CrossRefGoogle Scholar
  54. 54.
    B. Bagley, Nature (London) 208, 674 (1965).CrossRefGoogle Scholar
  55. 55.
    A.L. Mackay, Acta Crystallogr. 15, 916 (1962).CrossRefGoogle Scholar
  56. 56.
    D. Levine and P.J. Steinhardt, Phys. Rev. Lett. 53, 2477 (1984).CrossRefGoogle Scholar
  57. 57.
    D.F. Rieck, R.A. Montag, T.S. Mechnie, and L.F. Dahl, J. Am. Chem. Soc. 108, 1330 (1986).CrossRefGoogle Scholar
  58. 58.
    A. Ceriotti, F. Demartin, P. Ingallina, M. Manassero, M. Marchionna, N. Masciocchi, and M. Sansoni, XIX Cong. Naz. Chim. Inorg., Cagliari, 189 (1986).Google Scholar
  59. 59.
    J.L. Vidal and J.M. Troup, J. Organomet. Chem. 213, 351 (1981).CrossRefGoogle Scholar
  60. 60.
    V.G. Albano, M. Sansoni, P. Chini, S. Martinengo, and D. Strumolo, J. Chem. Soc., Dalton Trans., 459 (1978).Google Scholar
  61. 61.
    D.M. Waschecheck, E.J. Wucherer, L.F. Dahl, A. Ceriotti, G. Longoni, M. Manassero, M. Sansoni, and P. Chini, J. Am. Chem. Soc. 101, 6110 (1979).CrossRefGoogle Scholar
  62. 62.
    A. Ceriotti, A. Fait, G. Longoni, G. Piro, L. Resconi, F. Demartin, M. Manassero, N. Masciocchi, and M. Sansoni, J. Am. Chem. Soc. 108, 5370 (1986).CrossRefGoogle Scholar
  63. 63.
    E.L. Muetterties and W.H. Knoth, Polyhedral Boranes, M. Dekker, New York (1968).Google Scholar
  64. 64.
    C.E. Briant, B.R. Theobald, J.W. White, L.K. Bell, D.M.P. Mingos, and A.J. Welch, J. Chem. Soc., Chem. Commun., 201 (1981).Google Scholar
  65. 65.
    B.K. Teo and K. Keating, J. Am. Chem. Soc. 106, 2224 (1984).CrossRefGoogle Scholar
  66. 66.
    J.C. Calabrese, L.F. Dahl, A. Cavalieri, P. Chini, G. Longoni, and S. Martinengo, J. Am. Chem. Soc. 96, 2616 (1974).CrossRefGoogle Scholar
  67. 67.
    J.C. Calabrese, L.F. Dahl, P. Chini, G. Longoni, and S. Martinengo, J. Am. Chem. Soc. 96, 2614 (1974).CrossRefGoogle Scholar
  68. 68.
    J.W. Lauher, J. Am. Chem. Soc. 100, 5305 (1978).CrossRefGoogle Scholar
  69. 69.
    K. Wade, Adv. Inorg. Chem. Radiochem. 18, 1 (1976).CrossRefGoogle Scholar
  70. 70.
    B.K. Teo, Inorg. Chem. 23, 1251 (1984).CrossRefGoogle Scholar
  71. 71.
    J.S. Bradley, Adv. Organomet. Chem. 22, 1 (1983).CrossRefGoogle Scholar
  72. 72.
    M. Tachikawa and E.L. Muetterties, Prog. Inorg. Chem. 28, 203 (1981).CrossRefGoogle Scholar
  73. 73.
    A. Ceriotti, F. Demartin, A. Fait, G. Longoni, M. Manassero, N. Masciocchi, G. Piro, and M. Sansoni, XVIII Cong. Naz. Chim. Inorg., Como, 137 (1985); J. Am. Chem. Soc. 108, 8091 (1986).Google Scholar
  74. 74.
    A.L. Bowman, G.P. Arnold, E.K. Storms, and N.G. Nereson, Acta Crystallogr. B28, 3102 (1972).Google Scholar
  75. 75.
    A. Andreini, Mem. Soc. Ital. Sci. 14, 75 (1907).Google Scholar
  76. 76.
    A.F. Wells, Three-Dimensional Nets and Polyedra, J. Wiley and Sons, New York, 145–148 (1977).Google Scholar
  77. 77.
    S. Nakagura, J. Phys. Soc. Japan 12, 482 (1957).CrossRefGoogle Scholar
  78. 78.
    E.M. Dry, Catalysis, Science and Technology, Springer-Verlag, Berlin, 1, 159 (1981).Google Scholar
  79. 79.
    G. Apai, J.F. Hamilton, J. Stohr, and A. Thompson, Phys. Rev. Lett. 43, 165 (1979).CrossRefGoogle Scholar
  80. 80.
    B. Moraweck, G. Clugnet, and A.J. Renouprez, Surf. Sci. 81, L631 (1979).CrossRefGoogle Scholar
  81. 81.
    A. Ceriotti, G. Longoni, G. Piro, L. Resconi, M. Manassero, N. Masciocchi, and M. Sansoni, J. Chem. Soc., Chem. Commun., 1402 (1985).Google Scholar
  82. 82.
    V.G. Albano, D. Braga, G. Ciani, and S. Martinengo, J. Organomet. Chem. 213, 293 (1981).CrossRefGoogle Scholar
  83. 83.
    V.G. Albano, P. Chini, S. Martinengo, M. Sansoni, and D. Strumolo, J. Chem. Soc., Dalton Trans., 459 (1978).Google Scholar
  84. 84.
    V.G. Albano, D. Braga, P. Chini, D. Strumolo, and S. Martinengo, J. Chem. Soc., Dalton Trans., 249 (1983).Google Scholar
  85. 85.
    D. Strumolo, C. Seregni, S. Martinengo, V.G. Albano, and D. Braga, J. Organomet. Chem. 252, C93 (1983).CrossRefGoogle Scholar
  86. 86.
    V.G. Albano, D. Braga, P. Chini, G. Ciani, and S. Martinengo, J. Chem. Soc., Dalton Trans., 645 (1982).Google Scholar
  87. 87.
    V.G. Albano, D. Braga, A. Fumagalli, and S. Martinengo, J. Chem. Soc., Dalton Trans., 1137 (1985).Google Scholar
  88. 88.
    H. Frohlich, Physica 4, 406 (1937).CrossRefGoogle Scholar
  89. 89.
    R. Kubo, J. Phys. Soc. Japan 17, 975 (1962).CrossRefGoogle Scholar
  90. 90.
    R. Denton, B. Muhlschlegel, and D.J. Scalapino, Phys. Rev. B7, 3589 (1973).Google Scholar
  91. 91.
    R. Kubo, A. Kanabata, and S. Kobayaski, Am. Rev. Matem. Sci. 14, 49 (1984).CrossRefGoogle Scholar
  92. 92.
    J.H. Sinfelt, Rev. Mod. Phys. 51, 569 (1979).CrossRefGoogle Scholar
  93. 93.
    R.F. Marzke, Catal. Rev. 19, 43 (1979).CrossRefGoogle Scholar
  94. 94.
    R.F. Marzke, W.S. Glaunsinger, and M. Bayard, Solid State Commun. 18, 1025 (1976).CrossRefGoogle Scholar
  95. 95.
    R.E. Benfield, P.P. Edwards, and A.M. Stacy, J. Chem. Soc., Chem. Commun., 525 (1982).Google Scholar
  96. 96.
    D.C. Johnson, R.E. Benfield, P.P. Edwards, W.J.H. Nelson, and M.D. Vargas, Nature (London) 314, 231 (1985).CrossRefGoogle Scholar
  97. 97.
    B.K. Teo, F.J. Di Salvo, J. Wasachek, G. Longoni, and A. Ceriotti, Inorg. Chem. 25, 2262 (1986).CrossRefGoogle Scholar
  98. 98.
    B.J. Pronk, H.B. Brom, L.J. De Jongh, G. Longoni, and A. Ceriotti, Solid State Commun. 59, 349 (1986).CrossRefGoogle Scholar
  99. 99.
    P. Biloen and W.M.H. Sachtler, Adv. Catal. 30, 165 (1981).CrossRefGoogle Scholar
  100. 100.
    M. Tachikawa and E.L. Muetterties, J. Am. Chem. Soc. 102, 4541 (1980).CrossRefGoogle Scholar
  101. 101.
    J.S. Bradley, G.B. Ansell, and E.W. Hill, J. Am. Chem. Soc. 101, 7417 (1979).CrossRefGoogle Scholar
  102. 102.
    J.W. Kolis, F. Basolo, and D.F. Shriver, J. Am. Chem. Soc. 104, 5626 (1982).CrossRefGoogle Scholar
  103. 103.
    A. Ceriotti, R. Della Pergola, G. Longoni, M. Manassero, and M. Sansoni, J. Chem. Soc., Dalton Trans., 1181 (1984).Google Scholar
  104. 104.
    G. Longoni, A. Ceriotti, R. Della Pergola, M. Manassero, M. Perego, G. Piro, and M. Sansoni, Philos. Trans. R. Soc. London, A 308, 47 (1982).CrossRefGoogle Scholar
  105. 105.
    G. Gervasio, R. Rossetti, P.L. Stanghellini, and G. Bor, Inorg. Chem. 23, 2073 (1984).CrossRefGoogle Scholar
  106. 106.
    A. Ceriotti, G. Longoni, M. Manassero, N. Masciocchi, L. Resconi, and M. Sansoni, J. Chem. Soc., Chem. Commun., 181 (1985).Google Scholar
  107. 107.
    A. Arrigoni, A. Ceriotti, R. Della Pergola, G. Longoni, M. Manassero, N. Masciocchi, and M. Sansoni, Angew. Chem., Int. Ed. Engl. 23, 322 (1984).CrossRefGoogle Scholar
  108. 108.
    A. Arrigoni, A. Ceriotti, R. Della Pergola, G. Longoni, M. Manassero, and M. Sansoni, J. Organomet. Chem. 296, 243 (1985).CrossRefGoogle Scholar
  109. 109.
    B.T. Heaton, G. Longoni, M. Marchionna, and G. Piro, unpublished work.Google Scholar
  110. 110.
    K.H. Whitmire and D.F. Shriver, J. Am. Chem. Soc. 102, 1956 (1980).CrossRefGoogle Scholar
  111. 111.
    M.A. Drezdzon and D.F. Shriver, J. Mol. Catal. 21, 81 (1983).Google Scholar
  112. 112.
    R.C. Brady III and R. Pettit, J. Am. Chem. Soc. 102, 6181 (1980).CrossRefGoogle Scholar
  113. 113.
    L.E. Toth, Transition Metal Carbides and Nitrides, Refractory Materials, v. 7, Academic Press, New York, London (1971).Google Scholar

Copyright information

© Kluwer Academic Publishers 1988

Authors and Affiliations

  1. 1.Dipartimento di Chimica Inorganica e Metallorganica e Centro del CNR per 10 Studio della Sintesi e della Struttura dei Composti dei Metalli di TransizioneUniversita’ di MilanoMilanoItaly

Personalised recommendations