Characterisation of edge-sharing decahalogenodiosmate complexes in multiple oxidation states; synthesis, magnetochemistry, voltammetry and associated spectroelectrochemistry of [PPh4]2[Os2(µ-X)2X8] (X = Br or Cl)[hair space]

(Note: The full text of this document is currently only available in the PDF Version )

Graham A. Heath, David G. Humphrey and Keith S. Murray


Abstract

Organo-soluble salts of the edge-sharing bioctahedral [Os2(µ-X)2X8]2– complexes (X = Br or Cl) have been prepared by an improved procedure and investigated electrochemically. Their solution redox behaviour spans five levels, [Os2(µ-X)2X8]z (z = 1–5), complementing pentavalent [Os2(µ-Cl)2Cl8] known only in the solid phase. Chilled solutions of electrogenerated [Os2(µ-X)2X8]3– and [Os2(µ-X)2X8]4– have been characterised by UV/VIS/NIR spectroscopy (213 K; 45 000 to 5000 cm–1). In contrast, [Os2(µ-X)2X8] and [Os2(µ-X)2X8]5– rearrange rapidly to the face-sharing nonahalides, [Os2(µ-X)3X6] and [Os2(µ-X)3X6]4–, losing ½ X2 or X as appropriate. The redetermined magnetic moments of the [Os2(µ-X)2X8]2– dimers (as their [PPh4]+ salts) are convergent at 1.52 and 1.48 µB per Os (296 K) for X = Br and Cl respectively. Cleavage reactions of [Os2(µ-X)2X8]z (X = Br or Cl) are valence-dependent, leading to [OsX5L] (L = MeCN) for z = 2, [OsX6]2– and trans-[OsX4L2] for z = 3, and exclusively trans-[OsX4L2] for z = 4.


References

  1. F. A. Cotton, S. A. Duraj, C. C. Hinckley, M. Matusz and W. J. Roth, Inorg. Chem., 1984, 23, 3080 CrossRef CAS.
  2. M. Bruns, M. Dartmann, G. Henkel, B. Krebs and W. Preetz, Z. Naturforsch., Teil. B, 1984, 39, 843 Search PubMed.
  3. F. A. Cotton, Polyhedron, 1987, 6, 667 CrossRef CAS.
  4. G. A. Heath and D. G. Humphrey, J. Chem. Soc., Chem. Commun., 1990, 672 RSC.
  5. D. G. Humphrey, Ph.D. Thesis, The Australian National University, 1992.
  6. M. Bruns and W. Preetz, Z. Anorg. Allg. Chem., 1986, 537, 88 CrossRef CAS.
  7. M. Bruns and W. Preetz, Z. Naturforsch., Teil B, 1986, 41, 25 Search PubMed.
  8. H. Hillebrecht, P. Hollmann, W. Preetz and G. Thiele, Z. Naturforsch., Teil. B, 1990, 45, 1416.
  9. K. Dehnicke, U. Muller and R. Weber, Inorg. Chem., 1984, 23, 2563 CrossRef CAS and refs. therein.
  10. W. Kelm and W. Preetz, Z. Anorg. Allg. Chem., 1989, 568, 117 CrossRef CAS.
  11. A. Wendt and W. Preetz, Z. Anorg. Allg. Chem., 1994, 620, 655 CrossRef CAS.
  12. P. Hollmann and W. Preetz, Z. Naturforsch., Teil B, 1992, 47, 1115 CAS.
  13. P. Hollmann and W. Preetz, Z. Anorg. Allg. Chem., 1992, 601, 47 CrossRef CAS.
  14. G. A. Heath, D. G. Humphrey, B. Moubaraki and K. S. Murray, unpublished work.
  15. B. N. Figgis and J. Lewis, Prog. Inorg. Chem., 1964, 6, 37 CAS.
  16. V. T. Coombe, G. A. Heath, T. A. Stephenson and D. K. Vattis, J. Chem. Soc., Dalton Trans., 1983, 2307 RSC.
  17. R. M. Christie, G. A. Heath, S. A. MacGregor, M. A. Schröder and L. J. Yellowlees, J. Chem. Soc., Chem. Commun., 1990, 1445 RSC.
  18. G. A. Heath and R. G. Raptis, Inorg. Chem., 1991, 30, 4106 CrossRef.
  19. S. P. Best, R. J. H. Clark and D. G. Humphrey, Inorg. Chem., 1995, 34, 1013 CrossRef CAS.
  20. R. J. H. Clark and D. G. Humphrey, Inorg. Chem., 1996, 35, 2053 CrossRef CAS.
  21. G. A. Heath, J. E. McGrady, R. G. Raptis and A. C. Willis, Inorg. Chem., 1996, 35, 6838 CrossRef CAS.
  22. B. D. Yeomans, D. G. Humphrey and G. A. Heath, J. Chem. Soc., Dalton Trans., 1997, 4153 RSC.
  23. R. S. Nicholson, Anal. Chem., 1966, 38, 1406 CrossRef CAS.
  24. R. C. Burns and T. A. O'Donnell, Inorg. Chem., 1979, 18, 3081 CrossRef CAS.
  25. C. Creutz, Prog. Inorg. Chem., 1983, 30, 1 CAS.
  26. D. E. Richardson and H. Taube, Coord. Chem. Rev., 1984, 60, 107 CrossRef CAS.
  27. W. Hermann, G. Huttner, I. Jibril, M. Koppen and K. Wieghardt, Z. Naturforsch., Teil. B, 1984, 39, 1335 Search PubMed.
  28. C. M. Duff and G. A. Heath, J. Chem. Soc., Dalton Trans., 1991, 2401 RSC.
  29. R. A. Walton, Coord. Chem. Rev., 1976, 21, 63 CrossRef CAS.
  30. J. E. McGrady, Ph.D. Thesis, The Australian National University, 1994.
  31. C. M. Duff and G. A. Heath, Inorg. Chem., 1991, 30, 2528 CrossRef CAS and refs. therein.
  32. A. B. P. Lever, Inorganic Electronic Spectroscopy, Elsevier, Amsterdam, 2nd edn., 1984 Search PubMed.
  33. H. Homborg, Z. Anorg. Allg. Chem., 1980, 460, 27 CrossRef CAS.
  34. H. G. Greulich and W. Preetz, J. Organomet. Chem., 1981, 220, 201 CrossRef CAS.
  35. G. A. Heath and D. G. Humphrey, J. Chem. Soc., Chem. Commun., 1991, 1668 RSC.
  36. E. König and G. König, Landolt Börnstein: Numerical Data and Functional Relationships in Science and Technology, Magnetic Properties of Co-ordination and Organometallic Transition Metal Compounds, New Series Group II, eds. K. H. Hellwege and A. M. Hellwege, Springer, Berlin, 1984, vol. 12a Search PubMed.
Click here to see how this site uses Cookies. View our privacy policy here.