Biimidazole complexes of ML22+ [M = Ru or Os, L = 2-(phenylazo)pyridine]. Synthesis, structure and redox properties of mono- and di-nuclear complexes[hair space]

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

Partha Majumdar, Shie-Ming Peng and Sreebrata Goswami


Abstract

A series of mono- and di-nuclear complexes of ruthenium and osmium containing the terminal ligands 2-(phenylazo)pyridine (pap), 2,2′-bipyridine (bpy) and the bridging ligand 2,2′-biimidazole(H2biim) have been prepared. The mononuclear complex [Ru(pap)2(H2biim)][ClO4]2·3CH2Cl2 was characterised by a single-crystal structure determination. The mononuclear complexes [M(pap)2(H2biim)]2+ (M = Ru or Os) act as dibasic acids and undergo deprotonation to afford [M(pap)2(Hbiim)]+ and [M(pap)2(biim)]. The completely deprotonated complexes behave as reactive building units (‘metal complex as ligand’) which react smoothly with metal complex units to produce homo- and hetero-dinuclear complexes. The structure of the dinuclear complex [Ru2(bpy)4(biim)][ClO4]2 was determined. Cyclic voltammetric studies on the above complexes were performed. The quasi-reversible half-wave potentials of the oxidation processes of the dinuclear complexes are dependent on the metal as well as on the nature of the terminal ligands. These undergo two one-electron oxidation processes centered at the metal. Partial oxidation of the dinuclear complexes led to unsymmetrical bridge cleavage to form monomeric complexes. Large numbers of ligand reduction responses were observed. In some cases the first ligand reduction occurs close to zero potential (with respect to the SCE).


References

  1. D. P. Rillema, R. Sahai, P. Matthews, A. K. Edwards, R. J. Shaver and L. Morgan, Inorg. Chem., 1990, 29, 167 CrossRef CAS.
  2. M. Haga, M. Md. Ali, S. Koseki, K. Fujimoto, A. Yoshimura, K. Nozaki, T. Ohno, K. Nakajima and D. J. Stufkens, Inorg. Chem., 1996, 35, 3335 CrossRef CAS and refs. therein.
  3. M. Haga, M. Md. Ali, H. Maegawa, K. Nozaki, A. Yoshimura and T. Ohno, Coord. Chem. Rev., 1994, 132, 99 CrossRef.
  4. M. Haga, M. Md. Ali and R. Arakawa, Angew. Chem., Int. Ed. Engl., 1996, 35, 76 CrossRef CAS.
  5. M. D. Ward, Chem. Soc. Rev., 1995, 121 RSC.
  6. K. Kalyanasundaram and Md. K. Nazeeruddin, Inorg. Chim. Acta, 1994, 226, 213 CrossRef CAS.
  7. F. Holmes, K. M. Jones and E. G. Torrible, J. Chem. Soc., 1961, 4790 RSC.
  8. (a) S. Goswami, R. N. Mukherjee and A. Chakravorty, Inorg. Chem., 1983, 22, 2825 CrossRef CAS; (b) B. K. Ghosh, A. Mukhopadhyay, S. Goswami, S. Ray and A. Chakravorty, Inorg. Chem., 1984, 23, 4633 CrossRef CAS; (c) R. A. Krause and K. Krause, Inorg. Chem., 1982, 21, 1714 CrossRef CAS; (d) S. Goswami, A. R. Chakravarty and A. Chakravorty, Inorg. Chem., 1982, 21, 2737 CrossRef CAS.
  9. S. Goswami, A. R. Chakravarty and A. Chakravorty, Inorg. Chem., 1983, 22, 602 CrossRef CAS.
  10. T. K. Mallick, P. K. Das, B. K. Roy and B. K. Ghosh, J. Chem. Res., 1993, (S), 374 Search PubMed.
  11. P. Ghosh and A. Chakravorty, J. Chem. Soc., Dalton Trans., 1985, 361 RSC.
  12. S. Goswami, A. R. Chakravarty and A. Chakravorty, Inorg. Chem., 1981, 20, 2246 CrossRef CAS; R. A. Krause and K. Krause, Inorg. Chem., 1980, 19, 2600 CrossRef CAS.
  13. B. K. Ghosh, S. Goswami and A. Chakravorty, Inorg. Chem., 1983, 22, 3358 CrossRef CAS.
  14. M. Kakoti, A. K. Deb and S. Goswami, Inorg. Chem., 1992, 31, 1302 CrossRef CAS; S. Choudhury, A. K. Deb and S. Goswami, Polyhedron, 1994, 13, 1063 CrossRef CAS; S. Choudhury, A. K. Deb, W. Kharmawphlang and S. Goswami, Proc. Indian Acad. Sci., 1994, 106, 665 Search PubMed; S. Choudhury, A. K. Deb and S. Goswami, J. Chem. Soc., Dalton Trans., 1994, 1305 RSC; W. Kharmawphlang, S. Choudhury, A. K. Deb and S. Goswami, Inorg. Chem., 1995, 34, 3826 CrossRef CAS; P. Majumdar, A. K. Ghosh, L. R. Falvello, S. M. Peng and S. Goswami, Inorg. Chem., in press Search PubMed.
  15. C. K. Johnson, ORTEP, Report ORNL-5138, Oak Ridge National Laboratory, Oak Ridge, TN, 1976.
  16. A. Seal and S. Ray, Acta Crystallogr., Sect. C, 1984, 40, 929 CrossRef.
  17. A. K. Mahapatra, B. K. Ghosh, S. Goswami and A. Chakravorty, J. Indian Chem. Soc., 1986, 63, 101 Search PubMed.
  18. S. W. Kaiser, R. B. Saillant, W. M. Butler and P. G. Rasmussen, Inorg. Chem., 1976, 15, 2681 CrossRef CAS.
  19. M. Haga, Inorg. Chim. Acta, 1983, 75, 29 CrossRef CAS.
  20. S. Belanger and A. L. Beauchamp, Inorg. Chem., 1996, 35, 7836 CrossRef CAS.
  21. P. J. Giordano and M. S. Wrighton, J. Am. Chem. Soc., 1979, 101, 2888 CrossRef CAS; M. Haga, Inorg. Chim. Acta, 1980, 45, L183 CrossRef CAS.
  22. G. Denti, S. Campagna, S. Serroni, M. Ciano and V. Balzani, J. Am. Chem. Soc., 1992, 114, 2944 CrossRef CAS; A. Juris, V. Balzani, F. Barigelletti, S. Campagna, P. Belser and A. von Zelewski, Coord. Chem. Rev., 1988, 84, 85 CrossRef CAS; S. Serroni and G. Denti, Inorg. Chem., 1992, 31, 4251 CrossRef CAS; G. D. Marco, A. Bartolotta, V. Ricevuto, S. Campagna, G. Denti, L. Sabatino and G. D. Rosa, Inorg. Chem., 1991, 30, 270 CrossRef.
  23. G. Giuffrida and S. Campagna, Coord. Chem. Rev., 1994, 135/136, 517 CrossRef.
  24. S. W. Kaiser, R. B. Saillant, W. M. Butler and P. G. Rasmussen, Inorg. Chem., 1976, 15, 2688 CrossRef CAS.
  25. M. Haga and A. M. Bond, Inorg. Chem., 1991, 30, 475 CrossRef CAS.
  26. B. P. Sullivan, D. J. Salmon, T. J. Meyer and J. Peedin, Inorg. Chem., 1979, 18, 3369 CrossRef CAS.
  27. A. A. Vlcek, Coord. Chem. Rev., 1982, 43, 39 CrossRef CAS.
  28. P. J. Giordano, C. R. Bock and M. S. Wrighton, J. Am. Chem. Soc., 1978, 100, 6960 CrossRef CAS.
  29. B. F. Fieselmann, D. N. Hendrickson and G. D. Stucky, Inorg. Chem., 1978, 17, 2078 CrossRef.
  30. K. Lehmstedt, Liebigs Ann. Chem., 1927, 456, 253 Search PubMed.
  31. S. K. Chandra, P. Basu, D. Ray, S. Pal and A. Chakravorty, Inorg. Chem., 1990, 29, 2423 CrossRef CAS.
  32. A. I. Vogel, Quantitative Inorganic Analysis, Longmans, Green and Co., London, 1953, p. 177 Search PubMed.
  33. E. J. King, Acid-Base Equilibria, Pergamon, Oxford, 1965, p. 226 Search PubMed.
  34. E. J. Gabe, Y. Le Page, P. S. White and F. L. Lee, Acta Crystallogr., Sect. A, 1987, 43, 5294.
Click here to see how this site uses Cookies. View our privacy policy here.