View PDF Version
 
DOI: 10.1039/A700483D (Paper) Reference Section for: J. Chem. Soc., Dalton Trans., 1997, 1607-1610

Synthesis and crystal structure of the subvalent mercury cluster [triangulo-Hg3(µ-dmpm)4][O 3SCF3]4 (dmpm = Me2PCH2PMe2)

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

Anna Mühlecker-Knoepfler, Ernst Ellmerer-Müller, Robert Konrat, Karl-Hans Ongania, Klaus Wurst and Paul Peringer

Abstract

The subvalent mercury cluster [triangulo-Hg3(µ-dmpm)4][O3 SCF3]4 [dmpm = bis(dimethylphosphino)methane], involving the +4/3 oxidation state of mercury, was formed by reaction of [Hg2]2+ with 2 equivalents of dmpm or by reduction of a mixture of [Hg(Me2SO)6][O3SCF3]2 and dmpm in the molar ratio 2∶4 with elemental Hg. The cation consists of a Hg3 triangle [Hg–Hg 276.68(14), 280.99(14) and 295.53(14) pm] in which two edges are bridged by one dmpm ligand and the third edge is doubly bridged by a pair of dmpm ligands. The three Hg atoms and the phosphorus atoms of the singly bridging dmpm ligands are nearly in a plane. The dihedral angles of the Hg3 triangle and the mean planes formed by the doubly bridged Hg atoms and the phosphorus atoms of the two bridging dmpm ligands respectively are 61 and 46°. The complex is fluxional on the 31P NMR time-scale at 81 MHz at ambient temperature due to intramolecular exchange between the two different types of dmpm ligands.

References

  1. L. H. Gade, Angew. Chem., Int. Ed. Engl., 1993, 32, 24 CrossRef.
  2. P. A. W. Dean, in Comprehensive Coordination Chemistry, ed. G. Wilkinson, Pergamon, Oxford, 1987, vol. 2, p. 1 Search PubMed.
  3. K. Brodersen and H.-U. Hummel, in Comprehensive Coordination Chemistry, ed. G. Wilkinson, Pergamon, Oxford, 1987, vol. 5, p. 1049 Search PubMed.
  4. G. Torsi and G. Mamantov, Inorg. Nucl. Chem. Lett., 1970, 6, 843 Search PubMed.
  5. G. Torsi, K. W. Fung, G. M. Begun and G. Mamantov, Inorg. Chem., 1971, 10, 2285 CrossRef CAS.
  6. C. G. Davies, P. A. W. Dean, R. J. Gillespie and P. K. Ummat, Chem. Commun., 1971, 782 Search PubMed.
  7. R. J. Gillespie and P. K. Ummat, Chem. Commun., 1971, 1168 Search PubMed.
  8. R. D. Ellison, H. A. Levy and K. W. Fung, Inorg. Chem., 1972, 11, 833 CrossRef CAS.
  9. B. D. Cutforth, C. G. Davies, P. A. W. Dean, R. J. Gillespie, P. R. Ireland and K. Ummat, Inorg. Chem., 1973, 12, 1343 CrossRef CAS.
  10. B. D. Cutforth, R. J. Gillespie and P. R. Ireland, J. Chem. Soc., Chem. Commun., 1973, 723 Search PubMed.
  11. B. D. Cutforth, R. J. Gillespie, P. R. Ireland, J. F. Sawyer and P. K. Ummat, Inorg. Chem., 1983, 22, 1344 CrossRef CAS.
  12. I. D. Brown, R. J. Gillespie, K. R. Morgan, J. F. Sawyer, K. J. Schmidt, Z. Tun, P. K. Ummat and J. E. Vekris, Inorg. Chem., 1987, 26, 689 CrossRef CAS.
  13. I. D. Brown, B. D. Cutforth, C. G. Davies, R. J. Gillespie, P. R. Ireland and J. E. Vekris, Can. J. Chem., 1974, 52, 791 CAS.
  14. N. D. Miro, A. G. MacDiarmid, A. J. Heeger, A. F. Garito and C. K. Chiang, J. Inorg. Nucl. Chem., 1978, 40, 1351 CrossRef CAS.
  15. Z. Tun and I. D. Brown, Acta Crystallogr., Sect. B, 1982, 38, 2321 CrossRef.
  16. Z. Tun, I. D. Brown and P. K. Ummat, Acta Crystallogr., Sect. C, 1984, 40, 1301 CrossRef.
  17. I. D. Brown, R. J. Gillespie, K. R. Morgan, Z. Tun and P. K. Ummat, Inorg. Chem., 1984, 23, 4506 CrossRef CAS.
  18. H. Kunkely and A. Vogler, Chem. Phys. Lett., 1993, 206, 467 CrossRef CAS.
  19. S. Scavnicar, Acta Crystallogr., 1956, 9, 956 CrossRef.
  20. K. Aurivillius and L. Folkmarson, Acta Chem. Scand., 1968, 22, 2529 CAS.
  21. K. Brodersen, G. Göbel and G. Liehr, Z. Anorg. Allg. Chem., 1989, 575, 145 CrossRef CAS.
  22. B. Hämmerle, E. P. Müller, D. L. Wilkinson, G. Müller and P. Peringer, J. Chem. Soc., Chem. Commun., 1989, 1527 RSC.
  23. P. A. W. Dean and D. G. Ibbott, Inorg. Nucl. Chem. Lett., 1975, 11, 119 Search PubMed.
  24. P. A. W. Dean and D. G. Ibbott, Can. J. Chem., 1976, 54, 177 CAS.
  25. D. V. Toronto, A. L. Balch and D. S. Tinti, Inorg. Chem., 1994, 33, 2507 CrossRef CAS.
  26. S. S. M. Ling, N. Hadj-Bagheri, L. Manojlović-Muir, K. W. Muir and R. J. Puddephatt, Inorg. Chem., 1987, 26, 231 CrossRef CAS; R. J. Puddephatt, L. Manojlović-Muir and K. W. Muir, Polyhedron, 1990, 9, 2967 CrossRef CAS.
  27. G. Ferguson, M. C. Jennings, H. A. Mirza and R. J. Puddephatt, Organometallics, 1990, 9, 1576 CrossRef CAS.
  28. A. Knoepfler-Mühlecker and P. Peringer, unpublished work.
  29. G. Ferguson, B. R. Lloyd and R. J. Puddephatt, Organometallics, 1986, 5, 344 CrossRef CAS.
  30. P. S. Pregosin and R. W. Kunz, 31P and 13C NMR of Transition Metal Phosphine Complexes, eds. P. Diehl, E. Fluck and R. Kosfeld, Springer, Berlin, 1979 Search PubMed.
  31. D. A. Morgenstern, C. C. Bonham, A. P. Rothwell, K. V. Wood and C. P. Kubiak, Polyhedron, 1995, 14, 1129 CrossRef CAS.
  32. P. Peringer, J. Inorg. Nucl. Chem., 1980, 42, 1501 CrossRef CAS.
  33. G. M. Sheldrick, SHELXS 86, program for crystal structure solutions, University of Göttingen, 1986.
  34. G. M. Sheldrick, SHELXL 93, program for refinement of crystal structures, University of Göttingen, 1993.
Click here to see how this site uses Cookies. View our privacy policy here.