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Chemistry of Tetraosmium Carbonyl Clusters with Phenylazopyridine Ligands: Synthesis, Structure and Electrochemistry

Abstract

Two new tetraosmium carbonyl clusters [Os4(μ-H)4(CO)11{η 1-NC5H4(N=N)C6H5}] (1) and [Os4(μ-H)4(CO)10{η 2-NC5H4(N=N)C6H5}] (2) were synthesized from the reaction of [Os4(μ-H)4(CO)12] with two equivalent of 2-phenylazopyridine ligand in dichloromethane at ambient temperature using trimethylamine-N-oxide as the decarbonylation reagent. Subsequent chromatographic purification led to the isolation of 1and 2as stable orange and blue solids in respectively 25 and 13% yields. Complex 1converted to 2in a 25% yield in refluxing chloroform. Treating a solution of [Os4(μ-H)4(CO)12] in dichloromethane with two equivalent of 3-phenylazopyridine led to the formation of another two new clusters [Os4(μ-H)4(CO)11{η 1-NC5H4(N=N)C6H5}] (3) and [Os4(μ-H)4(CO)10(NMe3){η 1-NC5H4(N=N)C6H5}] (4), which could be isolated as yellow solids in 34% and 21% yields respectively. Thermolysis of 3or 4in refluxing n-hexane gives [Os4(μ-H)3(CO)10{μ-η 3-NC5H3(N=N)C6H5}] (5) in 24 and 33% yields respectively. Their electronic absorption properties and electrochemical behavior are also reported.

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REFERENCES

  1. 1.

    B. Hansert, M. Tasi, A. Tiripicchio, M. T. Camellini, and H. Vahrenkamp (1991). Organometallics 10, 4070.

    Google Scholar 

  2. 2.

    M. Tasi, A. K. Powell, and H. Vahrenkamp (1991). Chem. Ber. 124, 1549.

    Google Scholar 

  3. 3.

    H. Bantel, B. Hansert, A. K. Powell, M. Tasi, and H. Vahrenkamp (1989). Angew. Chem. Int. Ed. Eng. 28, 1509.

    Google Scholar 

  4. 4.

    J. A. Smieja, J. E. Gozum, and W. L. Gladfelter (1987). Organometallics 6, 1311.

    Google Scholar 

  5. 5.

    B. Hansert and H. Vahrenkamp (1993). Chem. Ber. 126, 2017.

    Google Scholar 

  6. 6.

    B. Hansert and H. Vahrenkamp (1993). Chem. Ber. 126, 2023.

    Google Scholar 

  7. 7.

    B. Hansert, A. K. Powell, and H. Vahrenkamp (1991). Chem. Ber. 124, 2697.

    Google Scholar 

  8. 8.

    F. S. Kong and W. T. Wong (1991). J. Organomet. Chem. 589, 180.

    Google Scholar 

  9. 9.

    J. A. Smieja, J. E. Gozum, and W. L. Gladfelter (1986). Organometallics 5, 2154.

    Google Scholar 

  10. 10.

    B. Hansert and H. Vahrenkamp (1993). Chem. Ber. 126, 2011.

    Google Scholar 

  11. 11.

    K. Majumder, S. M. Peng, and Samaresh Bhattacharya (2001). J. Chem. Soc., Dalton Trans.284.

  12. 12.

    M. I. Bruce, M. G. Humphrey, O. B. Shawkataly, M. R. Snow, and E. R. T. Tiekink (1987). J. Organomet. Chem. 336, 199.

    Google Scholar 

  13. 13.

    E. J. Wucherer, M. Tasi, B. Hansert, A. K. Powell, M. T. Garland, J. F. Halet, J. Y. Saillard, and H. Vahrenkamp (1989). Inorg. Chem. 28, 3564.

    Google Scholar 

  14. 14.

    Y. K. Au, K. K. Cheung, and W. T. Wong (1995). Inorg. Chim. Acta 238, 193.

    Google Scholar 

  15. 15.

    W. T. Wong and T. S. Wong (1997). J. Organomet. Chem. 542, 29.

    Google Scholar 

  16. 16.

    Y. Y. Choi and W. T. Wong (1999). J. Organomet. Chem. 573, 189.

    Google Scholar 

  17. 17.

    K. S. Y. Leung and Y. Li (1999). Inorg. Chem. 2, 599.

    Google Scholar 

  18. 18.

    Y. Li, Z. Y. Lin, and W. T. Wong (2001). Eur. J. Inorg. Chem.

  19. 19.

    C. Zuccaro, G. Pampaloni, and F. Calderazzo (1989). Inorg. Synth. 26, 169.

    Google Scholar 

  20. 20.

    Y. Y. Choi (1998). Ph.D. thesis, The University of Hong Kong.

  21. 21.

    R. D. Adams, J. E. Babin, and H. S. Kim (1986). Inorg. Chem. 25, 1122.

    Google Scholar 

  22. 22.

    B. F. G. Johnson, J. Lewis, P. R. Raithby, and C. Zuccaro (1979). J. Chem. Soc., Chem. Commum.916.

  23. 23.

    N. E. Leadbeater, J. Lewis, P. R. Raithby, and G. N. Ward (1997). J. Chem. Soc., Dalton Trans.2511.

  24. 24.

    A. J. Deeming, R. Peters, M. B. Hursthouse, and J. D. J. Backer-Dirks (1982). J. Chem. Soc., Dalton Trans.787.

  25. 25.

    C. E. Housecroft, personal communication.

  26. 26.

    W. Y. Wong, S. Chan, and W. T. Wong (1995). J. Organomet. Chem. 493, 229.

    Google Scholar 

  27. 27.

    W. Y. Wong and W. T. Wong (1996). J. Chem. Soc., Dalton Trans., 1853.

  28. 28.

    F. Effenberger and F. Wurthner (1993). Angew. Chem. Int. Ed. Engl. 32, 719.

    Google Scholar 

  29. 29.

    E. Buncel and S. Rajagopal (1990). Acc. Chem. Res. 23, 226.

    Google Scholar 

  30. 30.

    J. Heinze (1984). Angew. Chem. Int. Ed. Engl. 11, 831.

    Google Scholar 

  31. 31.

    S. E. Kabir, E. Rosenberg, L. Milone, R. Gobetto, D. Osella, M. Ravera, T. McPhillips, M. W. Day, D. Carlot, S. Hajela, E. Wolf, and K. Hardcastle (1997). Organometallics 16, 2674.

    Google Scholar 

  32. 32.

    D. Osella, G. Arman, M. Botta, R. Gobetto, F. Laschi, and P. Zanello (1989). Organometallics 8, 620.

    Google Scholar 

  33. 33.

    D. Osella, G. Arman, M. Botta, R. Gobetto, F. Laschi, P. Zanello, S. Ayrton, V. Goodfellow, C. E. Housecroft, and S. M. Owen (1989). Organometallics 8, 2689.

    Google Scholar 

  34. 34.

    D. D. Perrin and W. L. F. Armarego, Purification of Laboratory Chemicals, 3rd ed. (Pergamon, Oxford, 1988).

    Google Scholar 

  35. 35.

    H. D. Karsz, S. A. R. Knox, J. W. Koepke, and R. B. Saillant (1971). J. Chem. Soc., Chem. Commum.477.

  36. 36.

    B. F. G. Johnson, J. Lewis, P. R. Raithby, G. M. Scheldrick, and K. Wong (1978). J. Chem. Soc., Dalton Trans.673.

  37. 37.

    E. V. Brown and G. R. Granneman (1975). J. Am. Chem. Soc. 97, 621.

    Google Scholar 

  38. 38.

    G. M. Sheldrick, (1985). SHELXS86, Crystallographic Computing 3(Oxford University Press), pp. 175-189.

    Google Scholar 

  39. 39.

    P. T. Beurskens, G. Admiraal, G. Beurskens, W. P. Bosman, R. de Gelder, R. Israel, and J. M. M. Smits (1994). DIRDIF94, The DIRDIF-94 program system, Technical Report of the Crystallography Laboratory, University of Nijmegen, The Netherlands.

    Google Scholar 

  40. 40.

    Crystal Structure Analysis Package(Molecular Structure Corporation, 1985 and 1992).

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Li, Y., Wong, WT. Chemistry of Tetraosmium Carbonyl Clusters with Phenylazopyridine Ligands: Synthesis, Structure and Electrochemistry. Journal of Cluster Science 12, 595–617 (2001). https://doi.org/10.1023/A:1014250416239

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  • electrochemistry
  • phenylazopyridine
  • osmium carbonyl cluster