Journal of Cluster Science

, Volume 21, Issue 3, pp 379–396 | Cite as

Routes to Higher Nuclearity Mixed-Metal Carbonyl Clusters Using the [Rh(η5-C5Me5)(NCMe)3]2+ Dication as a Building Block

  • Saifun Nahar
  • John E. Davies
  • Gregory P. Shields
  • Paul R. Raithby
Original Paper

Abstract

Reaction of the [Rh(η5-C5Me5)(NCMe)3]2+ (1) dication with the hexaosmium [Os6(CO)17]2− (2) dianion leads to the initial formation of [Os6(CO)17Rh(η5-C5Me5)] (3). This cluster readily adds CO to form [Os6(CO)18Rh(η5-C5Me5)] (4) which has been characterised crystallographically. 3 also adds dihydrogen to give [Os6H2(CO)17Rh(η5-C5Me5)] (5) and undergoes a substitution reaction with PPh3 to form [Os6(CO)16(PPh3)Rh(η5-C5Me5)] (6). With the [Ru6(CO)18]2− (7) dianion, [Rh(η5-C5Me5)(NCMe)3]2+ (1) reacts to form three mixed-metal clusters [Ru5(CO)15Rh(η5-C5Me5)] (8), [Ru6(CO)18Rh(η5-C5Me5)] (9) and [Ru6(CO)18Rh25-C5Me5)2] (10). The clusters have been characterised spectroscopically and the structures of 8 and 10 have been confirmed crystallographically. The cluster 8 undergoes a substitution reaction with P(OMe)3 to form the disubstituted product [Ru5(CO)13(P(OMe)3)2Rh((η5-C5Me5)] (11) which has also been characterised crystallographically.

Keywords

Cluster carbonyl Rhodium Osmium Ruthenium Cyclopentadienyl X-ray crystal structure 

Notes

Acknowledgments

We gratefully acknowledge the support of the Cambridge Commonwealth Trust and the United Kingdom Committee of Vice Chancellors and Principals (to S. N.) and the Cambridge Crystallographic Data Centre (to G. P. S.). We are also grateful to the EPSRC for a Senior Fellowship (to P. R. R.).

References

  1. 1.
    P. Braunstein, L. A. Oro and P. R. Raithby (eds.) Metal Clusters in Chemistry (Wiley-VCH, Weinheim, 1999).Google Scholar
  2. 2.
    M. J. Ingleson, M. F. Mahon, P. R. Raithby, and A. S. Weller (2004). J. Am. Chem. Soc. 126, 4784.CrossRefGoogle Scholar
  3. 3.
    S. K. Brayshaw, M. J. Ingleson, J. C. Green, J. S. McIndoe, P. R. Raithby, G. Kociok-Kohn, and A. S. Weller (2006). J. Am. Chem. Soc. 128, 6247.CrossRefGoogle Scholar
  4. 4.
    S. K. Brayshaw, J. C. Green, R. Edge, E. J. L. McInnes, P. R. Raithby, J. E. Warren, and A. S. Weller (2007). Angew. Chem. Int. Ed. 46, 7844.CrossRefGoogle Scholar
  5. 5.
    J. Lewis and P. R. Raithby (1995). J. Organomet. Chem. 500, 227.CrossRefGoogle Scholar
  6. 6.
    S. R. Drake, B. F. G. Johnson, J. Lewis, W. J. H. Nelson, M. D. Vargas, T. Adatia, D. Braga, K. Henrick, M. McPartlin, and A. Sironi (1989). J. Chem. Soc., Dalton Trans. 1455.Google Scholar
  7. 7.
    O. A. Belyakova and Y. L. Slovokhotov (2003). Russ. Chem. Bull. 52, 2299.CrossRefGoogle Scholar
  8. 8.
    M. Kawano, J. W. Bacon, C. F. Campana, and L. F. Dahl (1996). J. Am. Chem. Soc. 118, 7869.CrossRefGoogle Scholar
  9. 9.
    H. Krautscheid, D. Fenske, G. Baum, and M. Semmelmann (1993). Angew. Chem. Int. Ed. Engl. 32, 1303.CrossRefGoogle Scholar
  10. 10.
    R. D. Adams, E. M. Boswell, B. Captain, A. B. Hungria, P. A. Midgley, R. Raja, and J. M. Thomas (2007). Angew. Chem. Int. Ed. 46, 8182.CrossRefGoogle Scholar
  11. 11.
    R. D. Adams, D. A. Blom, B. Captain, R. Raja, J. M. Thomas, and E. Trufan (2008). Langmuir 24, 9223.CrossRefGoogle Scholar
  12. 12.
    J. M. Thomas, R. D. Adams, E. M. Boswell, B. Captain, H. Gronbeck, and R. Raja (2008). Faraday Discuss. 138, 301.CrossRefGoogle Scholar
  13. 13.
    T. Nakajima, H. Konomoto, H. Ogawa, and Y. Wakatsuki (2007). J. Organomet. Chem. 692, 4886.CrossRefGoogle Scholar
  14. 14.
    L. H. Gade, B. F. G. Johnson, J. Lewis, M. McPartlin, H. R. Powell, P. R. Raithby, and W. T. Wong (1994). J. Chem. Soc., Dalton Trans. 521.Google Scholar
  15. 15.
    L. H. Gade, B. F. G. Johnson, J. Lewis, M. McPartlin, H. R. Powell, P. R. Raithby, and W.-T. Wong (1994). J. Chem. Soc., Dalton Trans. 521.Google Scholar
  16. 16.
    A. J. Amoroso, L. H. Gade, B. F. G. Johnson, J. Lewis, P. R. Raithby, and W. T. Wong (1991). Angew Chem. Int. Ed. Engl. 30, 107.CrossRefGoogle Scholar
  17. 17.
    J. Lewis, C. K. Li, M. C. Ramirez de Arellano, P. R. Raithby, and W. T. Wong (1993). J. Chem. Soc., Dalton Trans. 1359.Google Scholar
  18. 18.
    R. Buntem, J. Lewis, C. A. Morewood, P. R. Raithby, M. C. Ramirez de Arellano, and G. P. Shields (1998). J. Chem. Soc., Dalton Trans. 1091.Google Scholar
  19. 19.
    P. J. Bailey, A. J. Blake, P. J. Dyson, B. F. G. Johnson, J. Lewis, and E. Parisini (1993). J. Organomet. Chem. 452, 175.CrossRefGoogle Scholar
  20. 20.
    W. Clegg, N. Feeder, A. M. M. Castro, S. Nahar, P. R. Raithby, G. P. Shields, and S. J. Teat (1999). J. Organomet. Chem. 573, 237.CrossRefGoogle Scholar
  21. 21.
    J. E. Davies, S. Nahar, P. R. Raithby, and G. P. Shields (1997). J. Chem. Soc., Dalton Trans. 13.Google Scholar
  22. 22.
    B. F. G. Johnson, J. Lewis, M. A. Peasall, and L. G. Scott (1991). J. Organomet. Chem. 402, C27.CrossRefGoogle Scholar
  23. 23.
    J. Lewis, C.-K. Li, C. A. Morewood, M. C. Ramirez de Arellano, P. R. Raithby, and W.-T. Wong (1994). J. Chem. Soc., Dalton Trans. 2159.Google Scholar
  24. 24.
    C. R. Eady, B. F. G. Johnson, J. Lewis, R. Mason, P. B. Hitchcock, and K. M. Thomas (1977). J. Chem. Soc., Chem. Commun. 385.Google Scholar
  25. 25.
    D. M. P. Mingos (1983). J. Chem. Soc., Chem. Commun. 706.Google Scholar
  26. 26.
    D. M. P. Mingos (1984). Acc. Chem. Res. 17, 311.CrossRefGoogle Scholar
  27. 27.
    C. Couture, D. H. Farrar, M. P. Gomez-Sal, B. F. G. Johnson, R. A. Kamarudin, J. Lewis, and P. R. Raithby (1986). Acta Crystallogr. C 42, 163.CrossRefGoogle Scholar
  28. 28.
    B. F. G. Johnson, R. A. Kamarudin, F. J. Lahoz, J. Lewis, and P. R. Raithby (1988). J. Chem. Soc., Dalton Trans. 1205.Google Scholar
  29. 29.
    M. McPartlin, C. R. Eady, B. F. G. Johnson, and J. Lewis (1976). J. Chem. Soc., Chem. Commun. 883.Google Scholar
  30. 30.
    C. R. Eady, P. F. Jackson, B. F. G. Johnson, J. Lewis, C. Malatesta, M. McPartlin, and W. J. H. Nelson (1980). J. Chem. Soc., Dalton Trans. 383.Google Scholar
  31. 31.
    R. D. Adams, J. E. Babin, and M. Tasi (1988). Inorg. Chem. 27, 2618.CrossRefGoogle Scholar
  32. 32.
    J. R. Galsworthy, C. E. Housecroft, A. J. Edwards, and P. R. Raithby (1995). J. Chem. Soc., Dalton Trans. 2935.Google Scholar
  33. 33.
    R. Mason, K. M. Thomas, and D. M. P. Mingos (1973). J Am. Chem. Soc. 95, 3802.CrossRefGoogle Scholar
  34. 34.
    W. Clegg, N. Feeder, S. Nahar, P. R. Raithby, G. P. Shields, and S. J. Teat (1998). New J. Chem. 22, 1111.CrossRefGoogle Scholar
  35. 35.
    C. White, A. Yates, and P. M. Maitlis (1992). Inorg. Synth. 29, 228.CrossRefGoogle Scholar
  36. 36.
    G. M. Sheldrick SHELXS-86. Program for Crystal Structure Solution (University of Gottingen, Gottingen, 1986).Google Scholar
  37. 37.
    G. M. Sheldrick (2008). Acta Crystallogr. A 64, 112.CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media, LLC 2010

Authors and Affiliations

  • Saifun Nahar
    • 1
  • John E. Davies
    • 1
  • Gregory P. Shields
    • 1
  • Paul R. Raithby
    • 1
    • 2
  1. 1.Department of ChemistryUniversity of CambridgeCambridgeUK
  2. 2.Department of ChemistryUniversity of BathBathUK

Personalised recommendations