Preparative Aspects of One-Dimensional Transition Metal Coordination Compounds

  • H. J. Keller
Part of the Nato Advanced Study Institutes Series book series (NSSB, volume 7)


The results of a chemical and physical investigation of known linear chain metal compounds with direct metal-to-metal contacts can be successfully used as a guideline in the directed synthesis of new linear chain transition metal complexes with strong intermolecular interactions. One-dimensional metallic behaviour of crystallized four-coordinate planar transition metal compounds with 8 d electrons is expected if small and strongly π electron-accepting equatorial ligands like carbon monoxide are used. I.r., 1H-n.m.r., 195Pt-n.m.r., e.s.r., u.v. and 193Ir-Mößbauer spectra show that increasing bulkiness and increasing electron donating properties of the (mostly organic) ligands considerably decrease the strength of the intermolecular metal interactions in all compounds. Planar transition metal complexes with less than 8 d electrons per metal seem to be far better suited for the formation of 1d metals. But because of the strong Lewis acid activity of the individual molecules in solution, the axial positions in the coordination sphere are blocked by donating solvent molecules. The self-association reaction necessary for the building of linear chains is prevented for this reason. Preparative procedures to overcome these problems are proposed. One of the “mixed valence” solids obtained contains a linear I-3chain in addition to the linear metal chain.


Linear Chain Transition Metal Complex Mixed Valence Strong Intermolecular Interaction Metallic Lustre 
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  1. 1.
    H. R. Zeller, Adv. Solid State Phys. 13, 31 (1973)CrossRefGoogle Scholar
  2. 2.
    Z. G. Soos, Ann. Rev. Phys. Chem. 25, (1974)Google Scholar
  3. 3.
    E. B. Jagubskii, M. L. Khidekel, Russ. Chem. Rev. 41, 1011 (1972)CrossRefGoogle Scholar
  4. 4.
    A. F. Garito and A. J. Heeger, ATP Conf. Proc. 10, 1476 (1973)Google Scholar
  5. 5.
    V. V. Walatka jr., M. M. Labes, J. H. Perlstein, Phys. Rev. Letters 31, 1139 (1973)CrossRefGoogle Scholar
  6. 6.
    R. Greene, NATO-ASI on “Low-dimensional cooperative phenomena” Starnberg, 1974Google Scholar
  7. 7.
    A. F. Garito, A. J. Heeger, Acc.Chem.Res. 7, 232 (1974)CrossRefGoogle Scholar
  8. 8.
    F. H. Herbstein, Perspect. Struct. Chem. 4, 166 (1971)Google Scholar
  9. 9.
    T. W. Thomas, A. E. Underhill, Chem. Soc. Rev., 1, 99 (1972)CrossRefGoogle Scholar
  10. 10.
    U. Thewalt, Z. Naturforsch. 29 h, 308 (1974)Google Scholar
  11. 11.
    Z. G. Soos, T. Z. Huang, J. S. Valentine and R. C. Hughes, Phys. Rev. B 8, 993 (1973)CrossRefGoogle Scholar
  12. 12.
    L. V. Interrante, Symposium on “Extended interactiors in linear chain compounds”, Los Angeles, 1974Google Scholar
  13. 13.
    K. Krogmann, Angew. Chem. 81, 10 (1969)CrossRefGoogle Scholar
  14. 14.
    W. A. Little, NATO-ASI on “Low-dimensional cooperative phenomena” Starnberg, 1974Google Scholar
  15. 15.
    M. L. Moreau-Colin, Struct. and Bond. 10, 167 (1972)CrossRefGoogle Scholar
  16. 16.
    J. W. Dart, M. K. Lloyd, R. Mason, J. A. McCleverty, J. C. S. Dalton, 1973, 2039Google Scholar
  17. 17.
    D. Baumann, Dissertation, Univ. Heidelberg, 1974Google Scholar
  18. 18.
    F. Mehran, B. A. Scott, Phys. Rev. Lett., 31, 99 (1973)CrossRefGoogle Scholar
  19. 19.
    N. A. Bailey, E. U. Coates, G. B. Robertson, F. Bo-nati, R. Ugo, Chem. Commun., 1967, 1041Google Scholar
  20. 20.
    R. Aderjan, H. Breer, H. J. Keller, H. H. Rupp, Z. Naturforsch. 28 b, 164 (1973)Google Scholar
  21. 21.
    R. Aderjan, H. J. Keller, Z. Naturforsch. 28 b, 500 (1973)Google Scholar
  22. 22.
    W. Hieber, H. Lagally, A. Mayr, Z. Anorg. Allg. Chem. 246, 138 (1941)CrossRefGoogle Scholar
  23. 23.
    R. E. Benson, U. S. Patent, 1966, 3–255–195Google Scholar
  24. 24.
    R. R. Bartkowski and B. Morosin, Phys. Rev. B 6, 4209 (1972)CrossRefGoogle Scholar
  25. 25.
    M. R. Fox and E. C. Lingafelter, Acta Cryst. 22, 943 (1967)CrossRefGoogle Scholar
  26. 26.
    T. S. Srivastava, J. L. Przybylinski and A. Nath, Inorg. Chem. 13, 1562 (1974)CrossRefGoogle Scholar
  27. 27.
    G. E. Dickinson, J. Amer. Chem. Soc., 44, 2404 (1922)CrossRefGoogle Scholar
  28. 28.
    H. P. Fritz, H. J. Keller, Z. Naturforsch., 20 b, 1145 (1965)Google Scholar
  29. 29.
    R. Lorentz, Dissertation, Univ. Heidelberg, 1974Google Scholar
  30. 30.
    H. H. Rupp, unpublished resultsGoogle Scholar
  31. 31.
    H. Isci, W. R. Mason, Inorg. Chem. 13 1175 (1974)CrossRefGoogle Scholar
  32. 32.
    K. L. Monteith, L. F. Ballard, C. G. Pitts, B. K. Klein, L. M. Slifkin, J. P. Collman, Solid State Comm., 6, 301 (1968)CrossRefGoogle Scholar
  33. 33.
    R. Aderjan, H. J. Keller, H. H. Rupp, Z. Naturforsch 29 a, (1974)Google Scholar
  34. 34.
    R. Aderjan, Dissertation, Univ. Heidelberg, 1973Google Scholar
  35. 35.
    R. Aderjan, H. J. Keller, H. H. Rupp, F. Wagner, U. Wagner, (to be published)Google Scholar
  36. 36.
    A. P. Ginsberg, R. L. Cohen, F. J. DiSalvo and K. W. West, J. Chem. Phys. 60, 2657 (1974)CrossRefGoogle Scholar
  37. 37.
    C. V. Banks, D. W. Barnum, J. Amer. Chem. Soc., 80, 3579 (1958)CrossRefGoogle Scholar
  38. 38.
    H. J. Keller, M. Megnamisi-Bélombé, to be publishedGoogle Scholar
  39. 39.
    L. Malatesta, F. Canziani, J. Inorg.•Nucl. Chem., 19, 81 (1961)CrossRefGoogle Scholar
  40. 40.
    L. I. Buravov, R. N. Stepanova, M. L. Khidekel and I. F. Shchegolev, Dokl. Akad, Nauk. SSR, 203, 819 (1972)Google Scholar
  41. 41.
    I. I. Chernaev and Z. M. Novozhenyuk, Russ. J. Inorg Chem. 11, 1398 (1966)Google Scholar
  42. 42.
    R. D. Gillard and G. Wilkinson, J. Chem. Soc. 1964, 2835Google Scholar
  43. 43.
    W. Gitzel, H. J. Keller, H. H. Rupp, K. Seibold, Z. Naturforsch., 27 b, 365 (1972)Google Scholar
  44. 44.
    M. Simek, Collect. Czech. Chem. Commun. 27, 337 (1962)Google Scholar
  45. 45.
    A. S. Foust and R. H. Soderberg, J. Amer. Chem. Soc. 89, 5507 (1967)CrossRefGoogle Scholar
  46. 46.
    H. J. Keller, K. Seibold, J. Amer. Chem. Soc., 93, 1309 (1971)CrossRefGoogle Scholar
  47. 47.
    H. Endres, H. J. Keller, M. Megnamisi-Bélombé, W. Moroni, D. Nöthe, Inorg. Nucl. Chem. Lett., 10, 467 (1974)CrossRefGoogle Scholar
  48. 48.
    H. Endres, H. J. Keller, M. Megnamisi-Bélombé, W. Moroni, H. Pritzkow and J. Weiss, Acta Cryst.Google Scholar
  49. 49.
    L. Malatesta, “Isocyanide Complexes of Metals”, J. Wiley, London, 1969Google Scholar
  50. 50.
    D. Baumann, H. Endres, H. J. Keller, J. Weiss, J.C.S. Chem. Comm., 1973, 853Google Scholar

Copyright information

© Springer Science+Business Media New York 1975

Authors and Affiliations

  • H. J. Keller
    • 1
  1. 1.Anorganisch-Chemisches InstitutUniversität HeidelbergHeidelberg 1GFR

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