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Russian Chemical Bulletin

, Volume 58, Issue 11, pp 2258–2265 | Cite as

Ion exchange in bimetallic cage copper organosiloxanes and the synthesis of polynuclear metal complexes containing Li and CuII atoms

  • N. V. Sergienko
  • A. A. Korlyukov
  • V. D. Myakushev
  • M. Yu. Antipin
  • B. G. Zavin
Full Articles

Abstract

The replacement of sodium (potassium) atoms by lithium in a series of bimetallic (“alkaline”) cage copper organosiloxanes was investigated. The reactions of cage CuII(Na) or CuII(K) derivatives of organometallosiloxanes (OMS) with LiCl afford the corresponding CuII(Li) derivatives. The rate and degree of replacement are mainly determined by the structure of the molecular cage of the starting OMS. In the case of globular-like bimetallic OMS of the general formula [RSiO2]12[Cu4M4] (R = Me, H2C=CH-(Vin), or Ph; M = Na or K), the ion exchange occurs under mild conditions at a high rate to give the corresponding CuII(Li) derivatives [RSiO2]12Cu4Li4 with the same structure (∼80% yield). Sandwich-like bimetallic OMS of the general formula [RSiO2]6[Cu4M4][RSiO2]6 (R = Ph or Vin; M = Na or K) react more slowly, the reaction proceeding stepwise. In the latter case, partial substitution products, viz., heterometallic sandwich complexes, for example, {[VinSiO2]6}2Cu4K2Li2, were isolated. The structures and compositions of the reaction products were studied by X-ray diffraction, gel permeation chromatography, and elemental analysis. The selectivity of the replacement of alkali metal atoms allows the synthesis of the desired globular or sandwich cage Cu(Li) metallosiloxanes, which are difficult to prepare.

Key words

cage organometallosiloxanes alkaline copper organosiloxanes containing lithium, sodium, or potassium atoms heterometallic complexes ion exchange reactions with LiCl 

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References

  1. 1.
    F. J. Feher, J. Am. Chem. Soc., 1986, 108, 3850.CrossRefGoogle Scholar
  2. 2.
    F. J. Feher, T. A. Budzichovski, K. J. Weller, J. Am. Chem. Soc., 1989, 111, 7288.CrossRefGoogle Scholar
  3. 3.
    F. J. Feher, J. F. Walzer, Inorg. Chem., 1990, 29, 1604.CrossRefGoogle Scholar
  4. 4.
    F. J. Feher, Th. A. Budzichovski, Polyhedron, 1995, 14, 3239.CrossRefGoogle Scholar
  5. 5.
    M. Crocker, R. H. M. Herold, A. G. Orpen, Chem. Commun., 1997, 2411.Google Scholar
  6. 6.
    F. Lui, K. D. John, B. L. Scott, R. T. Baker, K. C. Ott, W. Tumas, Angew. Chem., Int. Ed., 2000, 39, 3127.Google Scholar
  7. 7.
    A. A. Zhdanov, N. V. Sergienko, E. S. Trankina, Izv. Akad. Nauk, Ser. Khim., 1998, 2530 [Russ. Chem. Bull. (Engl. Transl.), 1998, 47, 2448].Google Scholar
  8. 8.
    V. A. Igonin, S. V. Lindeman, Yu. T. Struchkov, O. I. Shchegolikhina, A. A. Zhdanov, Yu. A. Molodtsova, I. V. Razumovskaya, Metalloorg. Khim., 1991, 4, 1355 [Organomet. Chem. USSR (Engl. Transl.), 1991, 4, 672].Google Scholar
  9. 9.
    V. A. Igonin, S. V. Lindeman, Yu. T. Struchkov, Yu. A. Molodtsova, O. I. Shchegolikhina, A. A. Zhdanov, Izv. Akad. Nauk, Ser. Khim., 1993, 752 [Russ. Chem. Bull. (Engl. Transl.), 1993, 42, 718].Google Scholar
  10. 10.
    A. A. Zhdanov, O. I. Shchegolikhina, Yu. A. Molodtsova, Izv. Akad. Nauk, Ser. Khim., 1993, 957 [Russ. Chem. Bull. (Engl. Transl.), 1993, 42, 917].Google Scholar
  11. 11.
    M. M. Levitsky, O. I. Shchegolikhina, A. A. Zhdanov, V. A. Igonin, Yu. E. Ovchinnikov, V. E. Shklover, Yu. T. Struchkov, J. Organomet. Chem., 1991, 401, 199.CrossRefGoogle Scholar
  12. 12.
    O. I. Shchegolikhina, A. A. Zhdanov, V. A. Igonin, Yu. E. Ovchinnikov, V. E. Shklover, Yu. T. Struchkov, Metalloorg. Khim., 1991, 4, 74 [Organomet. Chem. USSR (Engl. Transl.), 1991, 4, 39].Google Scholar
  13. 13.
    A. R. Arutyunov, M. M. Levitskii, A. L. Buchachenko, N. V. Karpilovskaya, Izv. Akad. Nauk, Ser. Khim., 1996, 2131 [Russ. Chem. Bull. (Engl. Transl.), 1996, 45, 2026].Google Scholar
  14. 14.
    S. V. Lindeman, O. I. Shchegolikhina, Yu. A. Molodtsova, A. A. Zhdanov, Acta Crystallogr., 1997, C53, 305.Google Scholar
  15. 15.
    Yu. E. Ovchinnikov, A. A. Zhdanov, M. M. Levitskii, V. E. Shklover, Yu. T. Struchkov, Izv. Akad. Nauk SSSR, Ser. Khim., 1986, 1206 [Bull. Acad. Sci. USSR, Div. Chem. Sci. (Engl. Transl.), 1986, 35, 1097].Google Scholar
  16. 16.
    B. G. Zavin, N. V. Sergienko, E. V. Gorodnichev, V. D. Myakushev, A. A. Korlyukov, M. Yu. Antipin, Mendeleev Commun., 2005, 6, 245.CrossRefGoogle Scholar
  17. 17.
    A. A. Zhdanov, N. V. Sergienko, E. S. Trankina, Ross. Khim. Zh., 2001, 45, 44 [Mendeleev Chem. J. (Engl. Transl.), 2001, 45, No. 4].Google Scholar
  18. 18.
    Yu. A. Molodtsova, Yu. A. Pozdnyakova, I. V. Blagodatskikh, A. S. Peregudov, O. I. Shchegolikhina, Izv. Akad. Nauk, Ser. Khim., 2003, 2577 [Russ. Chem. Bull., Int. Ed., 2003, 52, 2722].Google Scholar
  19. 19.
    N. V. Sergienko, E. S. Trankina, V. I. Pavlov, A. A. Zhdanov, K. A. Lyssenko, M. Yu. Antipin, E. I. Akhmet’eva, Izv. Akad. Nauk, Ser. Khim., 2004, 337 [Russ. Chem. Bull., Int. Ed., 2004, 53, 351].Google Scholar
  20. 20.
    B. G. Zavin, E. V. Gorodnichev, L. V. Filimonova, N. V. Sergienko, A. A. Korlyukov, Tez. dokl., 10-i Vseros. konf. “Kremniiorganicheskie soedineniya: sintez, svoistva, primenenie”. [Abstrs. of Papers, 10th All-Russian Conf. “Organo- silicon Compounds: Synthesis, Properties, and Application”.] (Moscow, May 26–30, 2005), Moscow, 2005, U5 (in Russian).Google Scholar
  21. 21.
    M. Lazell, M. Motevalli, S. A. A. Shah, C. K. S. Simon, A. C. Sullivan, J. Chem. Soc., Dalton Trans., 1996, 1449.Google Scholar
  22. 22.
    O. I. Shchegolikhina, Yu. A. Molodtsova, Yu. A. Pozdnyakova, T. V. Strelkova, A. A. Zhdanov, Dokl. Akad. Nauk, 1992, 325, 1186 [Dokl. Chem. (Engl. Transl.), 1992].Google Scholar
  23. 23.
    I. V. Blagodatskikh, O. I. Shchegolikhina, Yu. A. Pozdnyakova, Yu. A. Molodtsova, A. A. Zhdanov, Izv. Akad. Nauk, Ser. Khim., 1994, 1057 [Russ. Chem. Bull. (Engl. Transl.), 1994, 43, 993].Google Scholar
  24. 24.
    B. G. Zavin, N. V. Sergienko, A. A. Korlyukov, V. D. Myakushev, M. Yu. Antipin, Mendeleev Commun., 2008, 18, 76.CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media, Inc.  2009

Authors and Affiliations

  • N. V. Sergienko
    • 1
  • A. A. Korlyukov
    • 1
  • V. D. Myakushev
    • 2
  • M. Yu. Antipin
    • 1
  • B. G. Zavin
    • 1
  1. 1.A. N. Nesmeyanov Institute of Organoelement CompoundsRussian Academy of SciencesMoscowRussian Federation
  2. 2.N. S. Enikolopov Institute of Synthetic Polymer MaterialsRussian Academy of SciencesMoscowRussian Federation

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