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Structures and fluxional behaviour of transition metal cluster carbonyls

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Conclusion

We have examined the structures of transition metal cluster carbonyls Mm(CO)n from the point of view of the geometrical arrangement of the carbonyl ligands, and, in particular, the polyhedra defined by their oxygen atoms. Provided that the metal atom cluster is reasonably spherical (which is presumed to be predetermined by electronic factors), these polyhedra correspond well to the ideal forms calculated by optimisation of mutual repulsions between points on a sphere. Thus the concepts of coordination polyhedra about single central atoms may be successfully applied to the coordination of carbonyl ligands about entire clusters of metal atoms. This is in contrast to the more usual emphasis on the environment of individual metal atoms in the cluster. In the fine balance of factors governing the structures of these molecules and anions, we believe that steric interaction between carbonyl groups is of greater importance than previously thought. The steric crowding of ligands around the central metal atom cluster has important implications for the reactivity and catalytic activity of cluster carbonyls. Additionally, a new approach to the fluxionality of these species, based on the idea that carbonyl mobility may occur by rearrangements of the entire ligand polyhedron, has led to new insights into the behaviour of a number of systems.

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References

  1. D. M. P. Mingos,Nature (Phys. Sci.), 236, 99 (1972);

    Google Scholar 

  2. K. Wade,Chem. Brit., 11, 177 (1975);Adv. Inorg. Chem. Radiochem., 18, 1 (1976);

    Google Scholar 

  3. R. B. King and D. H. Rouvray,J. Am. Chem. Soc., 99, 7834 (1977);

    Google Scholar 

  4. J. W. Lauher,J. Am. Chem. Soc., 100, 5305 (1978).

    Google Scholar 

  5. J. Lewis and B. F. G. Johnson,Pure Appl. Chem., 44, 43 (1974)

    Google Scholar 

  6. J. J. Rafalko, J. Lieto, B. C. Gates and G. L. Schrader,J. Chem. Soc. Chem. Comm., 540 (1978)

  7. R. Whyman, in B. F. G. Johnson (Ed.),Transition Metal Clusters, Wiley, London, 1980, p. 546.

    Google Scholar 

  8. M. Ichikawa,J. Chem. Soc. Chem. Comm., 566 (1978);

  9. G. C. Demitras and E. L. Muetterties,J. Am. Chem. Soc., 99, 2796 (1978);

    Google Scholar 

  10. A. K. Smith, F. Hugues, A. Theolier, J. M. Basset, R. Ugo, G. M. Zanderighi, J. L. Bilhou, V. Bilhou-Bougnol and W. F. Graydon, Inorg. Chem., 18, 3104 (1979);

    Google Scholar 

  11. W. E. Walker and R. M. Pruett (Union Carbide Corp.), Ger. Patent 2, 426, 411 (1975).Vide Chem. Abstr., 82, 139311p.

  12. R. M. Laine, R. G. Rinker and P. C. Ford,J. Am. Chem. Soc., 99, 252 (1978).

    Google Scholar 

  13. E. Band and E. L. Muetterties, Chem. Rev.78, 639 (1978)

    Google Scholar 

  14. R. E. Benfield and B. F. G. Johnson, in B. F. G. Johnson (Ed.),Transition Metal Clusters, Wiley, London, 1980, p. 472.

    Google Scholar 

  15. E. L. Eliel, N. L. Allinger, S. J. Angyal and G. A. Morrison,Conformational Analysis, Interscience, New York, 1965.

    Google Scholar 

  16. R. S. Nyholm and R. J. Gillespie,Quart. Rev. Chem. Soc., 11, 339 (1957).

    Google Scholar 

  17. P. B. Ryan and H. D. Todd,J. Chem. Phys., 67, 4787 (1977)

    Google Scholar 

  18. M. B. Hall,J. Am. Chem. Soc., 100, 6333 (1978)

    Google Scholar 

  19. A. Schmiederkamp, D. W. J. Cruickshank, S. Skaarup, P. Pulay, I. Hargittai and J. E. Boggs,J. Am. Chem. Soc., 101, 2002 (1979).

    Google Scholar 

  20. T. A. Claxton and G. C. Benson,Canad. J. Chem., 44, 157 (1956).

    Google Scholar 

  21. E. L. Muetterties and L. J. Guggenberger,J. Am. Chem. Soc., 98, 7221 (1976)

    Google Scholar 

  22. J. K. Kouba and S. S. Wreford,Inorg. Chem., 15, 1463 (1976)

    Google Scholar 

  23. B. E. Robertson,Inorg. Chem., 16, 2735 (1977).

    Google Scholar 

  24. E. L. Muetterties and L. H. Knoth,Polyhedral Boranes, Arnold, London, 1968.

    Google Scholar 

  25. F. C. Frank and J. S. Kasper,Acta Crystallogr., 11, 184 (1958).

    Google Scholar 

  26. E. L. Muetterties,Rec. Chem. Progr., 31, 51 (1970).

    Google Scholar 

  27. B. Eriksson, L. O. Larsson and L. Niinistö,J. Chem. Soc. Chem. Comm., 616 (1978).

  28. L. F. Dahl and J. M. Blount,Inorg. Chem., 4, 1373 (1966).

    Google Scholar 

  29. R. J. Doedens and L. F. Dahl,J. Am. Chem. Soc., 88, 4847 (1966).

    Google Scholar 

  30. P. Chini,Inorg. Chim. Acta Rev., 2, 31 (1968).

    Google Scholar 

  31. P. Chini, G. Longoni and V. G. Albano,Adv. Organometal Chem., 14, 285 (1976).

    Google Scholar 

  32. B. F. G. Johnson,J. Chem. Soc. Chem. Comm., 211 (1976).

  33. P. B. Hitchcock, R. Mason and M. Textor,J. Chem. Soc. Chem. Comm., 1047 (1976).

  34. F. A. Cotton and D. L. Hunter,Inorg. Chim. Acta, 11, L9 (1974).

    Google Scholar 

  35. V. G. Albano, P. L. Bellon and V. Scatturin,J. Chem. Soc. Chem. Comm., 730 (1967).

  36. F. A. Cotton and J. M. Troup,J. Am. Chem. Soc., 96, 4155 (1974).

    Google Scholar 

  37. D. J. Dahm and R. A. Jacobson,J. Am. Chem. Soc., 90, 5106 (1968).

    Google Scholar 

  38. G. Raper and W. S. McDonald, J. Chem. Soc. A, 3430 (1971).

    Google Scholar 

  39. R. E. Benfield and B. F. G. Johnson,J. Chem. Soc. Dalton Trans., 1743 (1980).

  40. A. J. Stone,Inorg. Chem., 20, 563 (1981).

    Google Scholar 

  41. L. Föppl,J. Reine Angew. Math., 141, 251 (1912).

    Google Scholar 

  42. H. Cohn,Math. Tables aids Comput., 10, 117 (1956).

    Google Scholar 

  43. M. Goldberg,Math. Comput., 23, 785 (1969).

    Google Scholar 

  44. R. B. King,J. Am. Chem. Soc., 92, 6460 (1970).

    Google Scholar 

  45. T. W. Melnyck, O. Knop and W. R. Smith,Canad. J. Chem., 55, 1745 (1977).

    Google Scholar 

  46. G. G. Sumner, H. P. Klug and L. E. Alexander,Acta Crystallogr., 17, 732 (1964).

    Google Scholar 

  47. G. Bör and K. Noack,J. Organometal Chem., 64, 367 (1974).

    Google Scholar 

  48. D. L. Lichtenberger and T. L. Brown,Inorg. Chem., 17, 1381 (1978).

    Google Scholar 

  49. H. B. Chin, M. B. Smith, R. D. Wilson and R. Bau,J. Am. Chem. Soc., 96, 5285 (1974).

    Google Scholar 

  50. F. A. Cotton and J. M. Troup,J. Chem. Soc. Dalton Trans., 800 (1974).

  51. S. C. Abrahams, A. P. Ginsberg and K. Knox,Inorg. Chem., 3, 558 (1964).

    Google Scholar 

  52. H. B. Chin and R. Bau,Inorg. Chem., 17, 2314 (1978).

    Google Scholar 

  53. L. F. Dahl and R. E. Rundle,Acta Crystallogr., 16, 419 (1963).

    Google Scholar 

  54. M. F. Bailey and L. F. Dahl,Inorg. Chem., 4, 1140 (1965).

    Google Scholar 

  55. L. F. Dahl, E. Ishishi and L. F. Rundle,J. Chem. Phys., 26, 1750 (1957).

    Google Scholar 

  56. N. I. Gapotchenko, N. V. Alekseev, N. E. Kolobova, K. N. Anisimov, I. A. Ronova and A. A. Johansson,J. Organometal Chem., 35, 319 (1972).

    Google Scholar 

  57. P. Lemoine, M. Gross and J. Boissier,J. Chem. Soc. Dalton Trans., 1626 (1972).

  58. F. H. Carré, F. A. Cotton and B. A. Frenz,Inorg. Chem., 15, 380 (1976).

    Google Scholar 

  59. V. G. Albano, G. Ciani and S. Martinengo,J. Organometal Chem., 78, 265 (1974).

    Google Scholar 

  60. C. H. Wei,Inorg. Chem., 8, 2384 (1969).

    Google Scholar 

  61. M. R. Churchill, F. J. Hollander and J. P. Hutchinson,Inorg. Chem., 16, 2655 (1977).

    Google Scholar 

  62. M. R. Churchill and B. G. DeBoer,Inorg. Chem., 16, 878 (1977).

    Google Scholar 

  63. M. R. Churchill and J. P. Hutchinson,Inorg. Chem., 17, 3528 (1978).

    Google Scholar 

  64. G. Longoni, P. Chini, L. D. Lower and L. F. Dahl,J. Am. Chem. Soc., 97, 5034 (1975).

    Google Scholar 

  65. J. C. Calabrese, L. F. Dahl, A. Cavalieri, P. Chini, G. Longoni and S. Martinengo,J. Am, Chem. Soc., 96, 2616 (1974).

    Google Scholar 

  66. J. C. Calabrese, L. F. Dahl, P. Chini, G. Longoni and S. Martinengo,J. Am. Chem. Soc., 96, 2614 (1974).

    Google Scholar 

  67. P. C. Steinhardt, W. L. Gladfelter, A. D. Harley, J. R. Fox and G. L. Geoffroy,Inorg. Chem., 19, 332 (1980).

    Google Scholar 

  68. M. Manassero, M. Sansoni and G. Longoni,J. Chem. Soc. Chem. Comm., 919 (1976).

  69. V. G. Albano, P. L. Bellon, P. Chini and V. Scatturin,J. Organometal Chem., 16, 461 (1969).

    Google Scholar 

  70. V. G. Albano, G. Ciani and P. Chini,J. Chem. Soc. Dalton Trans., 432 (1974).

  71. V. G. Albano, P. Chini and V. Scatturin,J. Organometal Chem., 15, 423 (1968).

    Google Scholar 

  72. V. G. Albano, M. Sansoni, P. Chini and S. Martinengo,J. Chem. Soc. Dalton Trans., 651 (1973).

  73. A. Fumagalli, S. Martinengo, P. Chini, A. Albanati, S. Bruckner and B. T. Heaton,J. Chem. Soc. Chem. Comm., 195 (1978).

  74. D. W. Hart, R. G. Teller, C.-Y. Wei, R. Bau, G. Longoni, S. Campanella, P. Chini and T. F. Koetzle,Angew. Chem. Int. Edit., 18, 80 (1979).

    Google Scholar 

  75. E. H. Braye, L. F. Dahl, W. Hübel and D. L. Wampler,J. Am. Chem. Soc., 84, 4633 (1962).

    Google Scholar 

  76. E. R. Corey, L. F. Dahl and W. Beck,J. Am. Chem. Soc., 85, 1202 (1963).

    Google Scholar 

  77. M. R. Churchill and J. Wormald,J. Chem. Soc. Dalton Trans., 2410 (1974).

  78. B. E. Reichert and G. M. Sheldrick,Acta Crystallogr., B33, 173 (1977).

    Google Scholar 

  79. J. K. Ruff, R. P. White and L. F. Dahl,J. Am. Chem. Soc., 93, 2159 (1971).

    Google Scholar 

  80. M. R. Churchill and R. Bau,Inorg. Chem., 7, 2606 (1968).

    Google Scholar 

  81. e.g. P. F. Jackson, B. F. G. Johnson, J. Lewis, M. McPartlin and W. J. H. Nelson,J. Chem. Soc. Chem. Comm., 735 (1979).

  82. R. S. Berry,J. Chem. Phys., 32, 933 (1960).

    Google Scholar 

  83. G. F. Stuntz and J. R. Shapley,J. Am. Chem. Soc., 99, 607 (1977).

    Google Scholar 

  84. B. F. G. Johnson, J. Lewis, B. E. Reichert and K. T. Schorpp,J. Chem. Soc. Dalton Trans., 1403 (1976).

  85. B. F. G. Johnson,J. Chem. Soc. Chem. Comm., 703 (1976).

  86. R. E. Benfield, P. D. Gavens, B. F. G. Johnson, M. J. Mays, L. Milone, S. Aime and D. Osella, submitted for publication:J. Chem. Soc. Dalton Trans.

  87. B. F. G. Johnson and R. E. Benfield,J. Chem. Soc. Dalton Trans., 1554 (1978).

  88. H. D. Kaesz, R. Bau, H. A. Beall and W. N. Lipscomb,J. Am. Chem. Soc., 89, 4218 (1967).

    Google Scholar 

  89. C. R. Eady, W. G. Jackson, B. F. G. Johnson, J. Lewis and T. W. Matheson,J. Chem. Soc. Chem. Comm., 958 (1975).

  90. C. A. Tolman,Chem. Rev., 77, 913 (1977).

    Google Scholar 

  91. J. R. Shapley, G. F. Stuntz, M. R. Churchill and J. P. Hutchinson,J. Chem. Soc. Comm., 219 (1979).

  92. M. I. Bruce, G. Shaw and F. G. A. Stone,J. Chem. Soc. Dalton Trans., 2094 (1972).

  93. R. E. Benfield, B. F. G. Johnson, P. R. Raithby and G. M. Sheldrick,Acta Crystallogr., B34, 666 (1978).

    Google Scholar 

  94. B. F. G. Johnson, J. Lewis, P. R. Raithby and J. Sedlmair, unpublished results.

  95. E. J. Forbes, N. Goodhand, D. L. Jones and T. A. Hamor,J. Organometal Chem., 182, 143 (1979).

    Google Scholar 

  96. R. E. Benfield, B. F. G. Johnson, J. Lewis, P. R. Raithby, C. Zuccaro and K. Henrick,Acta Crystallogr., B35, 2210 (1979).

    Google Scholar 

  97. A. G. Orpen, A. V. Rivera, E. G. Bryan, D. Pippard and G. M. Sheldrick,J. Chem. Soc. Chem. Comm., 723 (1978).

  98. R. D. Adams and N.M. Golombeski,Inorg. Chem., 18, 1909 (1979).

    Google Scholar 

  99. P. Chini,Gazz. Chim. Ital, 109, 225 (1979).

    Google Scholar 

  100. P. A. Dawson, B. F. G. Johnson, J. Lewis, D. A. Kaner and P. R. Raithby,J. Chem. Soc. Chem. Comm., 961 (1980).

  101. V. G. Albano, P. Chini, E. Ciani, M. Sansoni and S. Martinengo,J. Chem. Soc. Dalton Trans., 163 (1980).

  102. P. E. Jaitner and K. E. Schwarzhans,Z. Naturforsch. Trans., 32B, 705 (1977).

    Google Scholar 

  103. M. I. Bruce, D. Schultz, R. C. Wallis and A. D. Redhouse,J. Organometal Chem., 169, C15 (1979).

    Google Scholar 

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    Robert E. Benfield & Brian F. G. Johnson

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Benfield, R.E., Johnson, B.F.G. Structures and fluxional behaviour of transition metal cluster carbonyls. Transition Met Chem 6, 131–144 (1981). https://doi.org/10.1007/BF00624332

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