Russian Chemical Bulletin

, Volume 42, Issue 6, pp 981–985 | Cite as

Redox properties of cobalt(II) and methylcobalt(III) complexes with dianionic macrocyclic polychelate ligands

  • Yu. E. Kovalenko
  • Ya. D. Lampeka
  • I. Ya. Levitin
  • K. B. Yatsimirskii
  • K. Muller
  • D. Seidel
  • E. -G. Jager
General and Inorganic Chemistry

Abstract

Redox potentials of a series of complexes of cobalt(II) and organocobalt(III) with tetraazamacrocyclic (N4) and N2O2-noncyclic polychelate ligands have been determined by cyclic voltammetry. Introduction of ano-phenylene fragment instead of an ethylene fragment into an equatorial ligand and/or exchange of an N4-coordination chromophore for the N2O2-analog has been shown to result in the anodic shift of redox potentials of MeCo(IV)L/ MeCo(III)L, MeCo(III)L/MeCo(II)L, and Co(II)L/Co(I)L pairs. It has been established that the solvent effect on redox potential is larger for Co(III)L/Co(II)L than for other pairs. Apparently, this is the first case when quasi-reversible stages of oxidation of MeCo(III)L to MeCo(IV)L+ and MeCo(IV)L+ to [MeCo(IV)L]2+ can be simultaneously observed. A. relatively stable complex of methylcobalt(IV) with a long lifetime at ∼20 °C has been registered by the ESR method.

Key words

organometallic compounds cobalt—carbon bond redox potentials cobalt(IV) 

Preview

Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.

References

  1. 1.
    A. M. Yurkevich and I. P. Rudakov,Results of Science and Technique, Bioorgan. Khimiya, Moscow, 1985,5, 198 (in Russian).Google Scholar
  2. 2.
    P. J. Toscano and L. G. Marzilli,Progr. Inorg. Chem., 1984,31, 105.Google Scholar
  3. 3.
    Yu. E. Kovalenko, Ya. D. Lampeka, K. B. Yatsimirskii, E.-G. Jager, K. Muller, and D. Seidel,Zh. Fiz. Khim., 1990,64, 2659 [J. Phys. Chem., 1990,64 (Engl. Transl.)].Google Scholar
  4. 4.
    D. Seidel,Beitrage zur Chemie macrocyclischer Chelatokomplexe und versandter Verbindungen, Dissertation, Jena, 1985.Google Scholar
  5. 5.
    E.-G. Jager, P. Renner, and R. Schmidt,Z. Chem., 1977,17, 307.Google Scholar
  6. 6.
    A. J. Gordon and R. A. Ford,The Chemist's Companion, Wiley-Interscience, New York-London-Sydney-Toronto, 1972.Google Scholar
  7. 7.
    G. A. Forcier and J. W. Olver,Anal. Chem., 1965,37, 1447.Google Scholar
  8. 8.
    C. M. Wheeler and R. A. Sandstedt,J. Am. Chem. Soc., 1955,77, 2024.Google Scholar
  9. 9.
    V. Alexander and V. V. Ramanujam,Inorg. Chim. Acta., 1989,156, 125.Google Scholar
  10. 10.
    E.-G. Jager, E. Hassler, M. Rudolf, and A. Schneider,Z. Anorg. Allg. Chem., 1985,525, 67.Google Scholar
  11. 11.
    E.-G. Jager, M. Rudolf, and D. Seidel,Z. Chem., 1985,25, 378.Google Scholar
  12. 12.
    R. S. Nicholson and I. Shain,Anal. Chem., 1964,36, 706.Google Scholar
  13. 13.
    D. Dodd and M. D. Johnson,Organomet. Chem. Rev., 1973,52, 232.Google Scholar
  14. 14.
    G. Costa, G. Mestroni, A. Puxeddu, and E. Reisenhofer,J. Chem. Soc. A., 1970, 2870.Google Scholar
  15. 15.
    A. Wolberg and J. Manassen,J. Am. Chem. Soc., 1970,92, 2982.Google Scholar
  16. 16.
    N. Takvoryann, K. Farrmery, and V. Katovic,J. Am. Chem. Soc., 1974,96, 731.Google Scholar
  17. 17.
    I. Vasilevskis and D. S. Olson,Inorg. Chem., 1971,10, 1228.Google Scholar
  18. 18.
    M. P. Liteplo and J. F. Endicott,Inorg. Chem., 1971,10, 1420.Google Scholar
  19. 19.
    J. Halpern, M. S. Chan, J. Hanson, T. S. Roche, and J. A. Topich,J. Am. Chem. Soc., 1975,97, 1606.Google Scholar
  20. 20.
    D. W. Clack and N. S. Hush,J. Am. Chem. Soc., 1965,87, 4238.Google Scholar
  21. 21.
    R. H. Felton and H. Linschitz,J. Am. Chem. Soc., 1966,88, 1113.Google Scholar
  22. 22.
    G. Costa,Coord. Chem. Rev., 1972,8, 63.Google Scholar
  23. 23.
    E.-G. Jager, M. Rudolf, and R. Muller,Z. Chem., 1978,18, 229.Google Scholar
  24. 24.
    A. B. P. Lever,Inorganic Electronic Spectroscopy, Amsterdam, Elsevier, 1984.Google Scholar
  25. 25.
    E.-G. Jager, P. Renner, and R. Schmidt,Z. Chem., 1977,77, 189.Google Scholar
  26. 26.
    J. Topich and J. Halpern,Inorg. Chem., 1979,18, 1339.Google Scholar
  27. 27.
    I. Ya. Levitin, A. L. Sigan, A. I. Prokof'ev, and M. E. Vol'pin,Dokl. Akad. Nauk SSSR, 1990,311, 370 [Dokl. Chem., 1990,311 (Engl. Transl.)].Google Scholar
  28. 28.
    M. E. Vol'pin, I. Ya. Levitin, A. L. Sigan, and A. T. Nicitaev,J. Organomet. Chem., 1985,289, 263.Google Scholar

Copyright information

© Plenum Publishing Corporation 1994

Authors and Affiliations

  • Yu. E. Kovalenko
    • 1
  • Ya. D. Lampeka
    • 1
  • I. Ya. Levitin
    • 1
  • K. B. Yatsimirskii
    • 1
  • K. Muller
    • 2
  • D. Seidel
    • 2
  • E. -G. Jager
    • 2
  1. 1.L. V. Pisarzhevskii Institute of Physical ChemistryUkrainian Academy of SciencesKievUkraine
  2. 2.Chemical DepartmentSchiller UniversityJenaGermany

Personalised recommendations