Russian Chemical Bulletin

, Volume 48, Issue 9, pp 1762–1766 | Cite as

New semiquinone-catecholate rhodium complex with 2,2′-dipyridyl

  • G. A. Abakumov
  • V. K. Cherkasov
  • M. P. Bubnov
  • L. G. Abakumova
  • L. N. Zakharov
  • G. K. Fukin
Organometallic Chemistry
  • 50 Downloads

Abstract

A new semiquinone rhodium complex,viz., (2,2′-dipyridyl)(3,6-di-tert-butyl-o-benzosemiquinone)(3,6-di-tert-butylcatecholate)rhodium(III) (1), which is a structural analog of the known redox-isomeric cobalt complex, was prepared, isolated in the individual state, and characterized by X-ray analysis, magnetochemistry, and IR and ESR spectroscopy. At room temperature, compound1, unlike the cobalt analog, is a complex of trivalent low-spin rhodium with one catecholate and one semiquinone ligand. However, broadening of the lines in the ESR spectra both of a solution and a powder of complex1 with increasing temperature indicates that the redox-isomeric transformation occurs in this case as well. The equilibrium of this transformation is virtually completely shifted toward the low-spin semiquinone-, catecholate isomer.

Key words

rhodium(III) o-semiquinone redox isomerism X-ray diffraction study ESR spectra 

Preview

Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.

References

  1. 1.
    R. M. Buchanan and C. G. Pierpont,J. Am. Chem. Soc., 1980,102, 4951.CrossRefGoogle Scholar
  2. 2.
    G. A. Abakumov, V. I. Nevodchikov, and V. K. Cherkasov,Dokl. Akad. Nauk SSSR, 1984,278, 641 [Dokl. Chem., 1984 (Engl. Transl.)].Google Scholar
  3. 3.
    C. G. Pierpont and C. W. Lange,Prog. Inorg. Chem., 1994,41, 331.Google Scholar
  4. 4.
    G. A. Abakumov, V. I. Nevodchikov, and V. K. Cherkasov,Izv. Akad. Nauk SSSR, Ser. Khim., 1986, 65 [Bull. Acad. Sci. USSR, Div. Chem. Sci., 1986,35, 54 (Engl. Transl.)].Google Scholar
  5. 5.
    G. A. Abakumov, V. K. Cherkasov, M. P. Bubnov, O. G. Ellert, Zh. V. Dobrokhotova, L. N. Zakharov, and Yu. T. Struchkov,Dokl. Akad. Nauk, 1993,328, 332 [Dokl. Chem., 1993 (Engl. Transl.)].Google Scholar
  6. 6.
    P. Gütlich and A. Dei,Angew. Chem., Int. Ed. Engl., 1997,36, 2734.CrossRefGoogle Scholar
  7. 7.
    D. Adams and D. N. Hendrickson,J. Am. Chem. Soc., 1996,118, 11515.CrossRefGoogle Scholar
  8. 8.
    C. G. Pierpont and O.-S. Jung,Inorg. Chem., 1995,34, 4281.CrossRefGoogle Scholar
  9. 9.
    C. Roux, D. M. Adams, J. P. Itie, A. Polian, D. N. Hendrickson, and M. Verdaguer,Inorg. Chem., 1996,35, 2846.CrossRefGoogle Scholar
  10. 10.
    G. A. Abakumov and V. I. Nevodchikov,Dokl. Akad. Nauk SSSR, 1982,266, 1407 [Dokl. Chem., 1982 (Engl. Transl.)].Google Scholar
  11. 11.
    C. W. Lange, M. Foldeaki, V. I. Nevodchikov, V. K. Cherkasov, G. A. Abakumov, and C. G. Pierpont,J. Am. Chem. Soc., 1992,114, 4220.CrossRefGoogle Scholar
  12. 12.
    O.-S. Jung and C. G. Pierpont,J. Am. Chem. Soc., 1994,116, 2229.CrossRefGoogle Scholar
  13. 13.
    V. I. Nevodchikov, G. A. Abakumov, V. K. Cherkasov, and G. A. Razuvaev,J. Organomet. Chem., 1981,214, 119.CrossRefGoogle Scholar
  14. 14.
    O.-S. Jung and C. G. Pierpont,Inorg. Chem., 1994,33, 2227.CrossRefGoogle Scholar
  15. 15.
    O.-S. Jung and C. G. Pierpont,J. Am. Chem. Soc., 1994,116, 1127.CrossRefGoogle Scholar
  16. 16.
    D. Adams, L. Noodleman, and D. N. Hendrickson,Inorg. Chem., 1997,36, 3966.CrossRefGoogle Scholar
  17. 17.
    C. G. Pierpont and R. M. Buchanan,Coord. Chem. Rev., 1981,38, 45.CrossRefGoogle Scholar
  18. 18.
    D. M. Adams, A. Dei, A. L. Rheindold, and D. N. Hendrickson,J. Am. Chem. Soc., 1993,115, 8221.CrossRefGoogle Scholar
  19. 19.
    L. N. Zakharov, Yu. T. Struchkov, G. A. Abakumov, and V. I. Nevodchikov,Koord. Khim., 1990,16, 1101 [Sov. J. Coord. Chem., 1990,16 (Engl. Transl.)].Google Scholar
  20. 20.
    J. Chatt and L. M. Venanzi,J. Chem. Soc., 1957, 4735.Google Scholar
  21. 21.
    V. A. Muraev G. A. Abakumov, and G. A. Razuvaev,Dokl. Akad. Nauk SSSR, 1974,217, 1083 [Dokl. Chem., 1974 (Engl. Transl.)].Google Scholar

Copyright information

© Kluwer Academic/Plenum Publishers 1999

Authors and Affiliations

  • G. A. Abakumov
    • 1
  • V. K. Cherkasov
    • 1
  • M. P. Bubnov
    • 1
  • L. G. Abakumova
    • 1
  • L. N. Zakharov
    • 1
  • G. K. Fukin
    • 1
  1. 1.G. A. Razuvaev Institute of Organometallic ChemistryRussian Academy of SciencesNizhnii NovgorodRussian Federation

Personalised recommendations