Russian Chemical Bulletin

, Volume 44, Issue 7, pp 1306–1310 | Cite as

Oxidation of isomeric η6- and η5-fluorenylchromiumtricarbonyl anions

  • L. N. Novikova
  • N. A. Ustynyuk
  • B. L. Tumanskii
  • P. V. Petrovskii
  • A. A. Borisenko
  • S. V. Kukharenko
  • V. V. Strelets
Organometallic Chemistry


The oxidation of the carbon-centered [(η6-C13H9)Cr(CO)3] anion (1) results in formation of (μ-η66-9,9′-bifluorenyl)bis-chromiumtricarbonyl (3) due to coupling of the intermediate carbon-centered radical (1.). The oxidation of the metal-centered anion [(η5-C13H9)Cr(CO)3] (2), which is isomeric to the 1 anion, gives an equilibrium mixture of the chromium-centered radical {(η5-C13H9)Cr(CO)3}. (2.) and its dimer [(η5-C13H9)Cr(CO)3]2 (6). Radical2. readily reacts with MeI and the solvent (THF); the resulting derivatives, (η5-C13H9)Cr(CO)3R (R=Me (10); R=H (7)), undergo fast ricochet inter-ring η5→η6 rearrangements into (η6-9R-C13H9)Cr(CO)3 (R=CH3 (9); R=H (4)).

Key words

transition metal complexes free radicals oxidation dimerization 


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  1. 1.
    M. C. Baird,Chem. Rev., 1988,88, 1217.Google Scholar
  2. 2.
    Organometallic Radical Process, Ed. W. C. Trogler, Elsevier, Amsterdam, 1990.Google Scholar
  3. 3.
    D. Astruc,Chem. Rev., 1988,88, 1189.Google Scholar
  4. 4.
    S. V. Kukharenko, V. V. Strelets, N. A. Ustynyuk, L. N. Novikova, L. I. Denisovich, and M. G. Peterleitner.Metalloorg. Khim., 1991,4, 299 [Organometal. Chem. USSR, 1991,4, 136 (Engl. Transl.)].Google Scholar
  5. 5.
    L. N. Novikova, B. A. Mazurchik, N. A. Ustynyuk, S. V. Kukharenko, and V. V. Strelets.Izv. Akad. Nauk, Ser. Khim., 1994, 319 [Russ. Chem. Bull., 1994,43, 299 (Engl. Transl.)].Google Scholar
  6. 6.
    S. V. Kukharenko, L. N. Novikova, V. V. Strelets, and N. A. Ustynyuk,Izv. Akad. Nauk, Ser. Khim., 1994, 48 [Russ. Chem. Bull., 1994,43, 41 (Engl. Transl.)].Google Scholar
  7. 7.
    B. G. Gribov, D. D. Mozzhukhin, B. I. Kozyrkin, and A. S. Strizhenova,Zh. Org. Khimii, 1972,42, 2531 [J. Org. Chem. USSR, 1972,42 (Engl. Transl.)].Google Scholar
  8. 8.
    F. I. Karol and R. N. Johnson,J. Polym. Sci., 1975, D13, 1607.Google Scholar
  9. 9.
    F. Rourke and J. A. Crayston,Chem. Communs., 1988, 1264.Google Scholar
  10. 10.
    F. Rourke, R. Crash, and J. A. Crayston,J. Organomet Chem., 1992,423, 223.Google Scholar
  11. 11.
    F. Bringewski, G. Huttner, W. Imhof, and L. Zsolhai,J. Organomet. Chem., 1992,439, 33.Google Scholar
  12. 12.
    Y. Zhang, D. K. Gosser, P. H. Rieger, and D. A. Sweigart,J. Am. Chem. Soc., 1991,113, 4062.Google Scholar
  13. 13.
    D. T. Pierce and W. E. Geiger,Inorg.Chem., 1974,33, 373.Google Scholar
  14. 14.
    K. A. E. O'Callagham, S. J. Brown, J. A. Page, M. C. Baird, T. C. Richards, and W. E. Geiger,Organometallics, 1991,10, 3119.Google Scholar
  15. 15.
    S. Fortier, M. C. Baird, K. F. Preston, J. R. Morton, T. Ziegler, T. J. Jalger, W. C. Watkins, J. H. MacNeil, K. A. Watson, K. Heusel, J. L. Page, J.-P. Charland, and A. J. Williams,J. Am. Chem. Soc., 1991,113, 542.Google Scholar
  16. 16.
    W. C. Watkins, T. Jalger, C. E. Kidd, S. Fortier, M. C. Baird, G. Kiss, G. C. Roper, and C. D. Hoff,J. Am. Chem. Soc., 1992,114, 907.Google Scholar
  17. 17.
    W. C. Watkins, K. Hensel, S. Fortier, D. H. Macartney, M. C. Baird, and J. C. Lain,Organometallics, 1992,11, 2418.Google Scholar
  18. 18.
    C. A. MacCounachie, J. M. Nelson, and M. C. Baird,Organometallics, 1992,11, 2521.Google Scholar
  19. 19.
    H. J. Keller,J. Naturforsch, 1968,236, 133.Google Scholar
  20. 20.
    R. J. Hoobler, M. A. Hutton, H. M. Dillard, M. P. Castellani, A. L. Reingold, A. L. Rieger, P. H. Rieger, T. C. Richards, and W. E. Geiger,Organometallics, 1993,12, 116.Google Scholar
  21. 21.
    R. B. King, M. Z. Igbal, and A. D. King, Jr.,J. Organomet. Chem., 1979,171, 53.Google Scholar
  22. 22.
    L. N. Novikova, Ph. D. Thesis (Chemistry),Inst. of Organoelement Compounds, Acad. Sci. USSR, Moscow, 1981 in Russian.Google Scholar
  23. 23.
    S. V. Kukharenko, G. L. Soloveichik, and V. V. Strelets,Izv. Akad. Nauk SSSR, Ser. Khim., 1986, 1020 [Bull. Acad. Sci. USSR, Div. Chem. Sci., 1986,35, 926 (Engl. Transl.)].Google Scholar
  24. 24.
    A. N. Nesmeyanov, N. A. Ustynyuk, L. G. Makarova, T. N. Rybina, Yu. A. Ustynyuk, Yu. F. Oprunenko, and O. I. Trifonova,J. Organomet. Chem., 1980,184, 63.Google Scholar
  25. 25.
    A. N. Nesmeyanov, N. A. Ustynyuk, L. G. Makarova, Steffen Andrae, Yu. A. Ustynyuk, L. N. Novikova, and Yu. N. Luzikov,J. Organomet. Chem., 1978,154, 45.Google Scholar

Copyright information

© Plenum Publishing Corporation 1995

Authors and Affiliations

  • L. N. Novikova
    • 1
  • N. A. Ustynyuk
    • 1
  • B. L. Tumanskii
    • 1
  • P. V. Petrovskii
    • 1
  • A. A. Borisenko
    • 1
  • S. V. Kukharenko
    • 2
  • V. V. Strelets
    • 2
  1. 1.A. N. Nesmeyanov Institute of Organoelement CompoundsRussian Academy of SciencesMoscowRussian Federation
  2. 2.Institute of Chemical Physics in ChernogolovkaRussian Academy of SciencesMoscow RegionRussian Federation

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