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Reaction of the framework 3d-organometallosiloxanes with acetylacetone

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Abstract

A reaction of acetylacetone with the framework sandwich-type metallosiloxanes (MOS) of general formula [PhSiO2]6M6[PhSiO2]6, where M = Cu, Ni, Mn, was studied by GPC, 1H and 29Si NMR spectroscopy, X-ray diffraction, elemental and functional analysis. The reaction involved replacement of the metal atoms with the hydrogen atoms and is accompanied by the formation of the corresponding chelate complexes M(acac)2. Displacement of the metal from the framework MOS leads to the destruction of molecular skeleton and formation of phenylsiloxanes containing Si-OH groups. The yield and composition of the reaction products considerably depend on the nature of the metal in [PhSiO2]6M6[ThSiO2]6. A selective substitution of the metal leads to the stereoregular hexahydroxyhexaphenylcyclohexasiloxane, [PhSiO(PH)]6, cis-isomer. The structure and composition of the crystalline hexahydroxyhexaphenylcyclohexasiloxane obtained were confirmed by 29Si NMR spectroscopy, X-ray diffraction study, and functional analysis, while its TMS derivative was studied with 1H NMR spectroscopy and GPC. Using a framework manganese phenylsiloxane as an example, a reversible character of the process has been established and an alternative synthesis of this compound from hexahydroxyhexaphenylcyclohexasiloxane and Mn(acac)2 has been accomplished for the first time.

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References

  1. A. A. Zhdanov, N. V. Sergienko, E. S. Trankina, Zh. Vseross. Khim. Obshch. im. D. I. Mendeleeva, 2001, 45, 44 [Mendeleev. Chem. J. (Engl. Transl.), 2001, 45].

    CAS  Google Scholar 

  2. 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 

  3. A. A. Zhdanov, L. I. Makarova, N. V. Sergienko, Izv. Akad. Nauk, Ser. Khim., 1998, 2527 [Russ. Chem. Bull. (Engl. Transl.), 1998, 47, 2445].

    Google Scholar 

  4. V. V. Smirnov, M. M. Levitskii, I. G. Tarkhanova, Zh. Vseross. Khim. Obshch. im. D. I. Mendeleeva, 2001, 45, 75 [Mendeleev. Chem. J. (Engl. Transl.), 2001, 45].

    CAS  Google Scholar 

  5. E. S. Obolonkova, L. I. Komarova, B. G. Zavin, V. S. Papkov, I. O. Volkov, M. I. Buzin, E. A. Trankina, N. V. Sergienko, in Struktura i dinamika molekulyarnykh sistem [Structure and Dinamics of Molecular Systems], KGU Publ., Kazan, 2007, p. 387 (in Russian).

    Google Scholar 

  6. A. A. Zhdanov, N. V. Sergienko, E. S. Trankina, Dokl. Akad. Nauk, 2000, 370, 50 [Dokl. Chem. (Engl. Transl.), 2000, 370, 1].

    CAS  Google Scholar 

  7. E. S. Trankina, N. V. Sergienko, O. G. Nikol’skii, V. A. Martirosov, Tez. dokl. Mezhdunarodnoi nauchno-tekhni-cheskoishkoly-konferentsii “Molodye uchenye — nauke, tekhnologiyam iprofessional’ nomu obrazovaniyu” [Abstr. International Scientific-technical School-Conference “Contribution of Young Scientists to Science, Technology, and Professional Education” (Moscow, October 1–4, 2003), Moscow, p. 122 (in Russian).

  8. A. D. Wilson, S. Crisp, in Organolithic Macromolecular Materials, Applied Science Publishers Ltd, London, 1974, p. 65.

    Google Scholar 

  9. C. W. Lentz, Inorg. Chem., 1964, 3, 574.

    Article  CAS  Google Scholar 

  10. O. I. Schchegolikhina, Yu. A. Pozdnyakova, Yu. A. Molodtsova, S. D. Korkin, S. S. Bukalov, L. A. Leites, K. A. Lysenko, A. S. Peregudov, N. Auner, D. E. Katsoulis, Inorg. Chem., 2002, 41, 6892.

    Article  Google Scholar 

  11. 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, 325].

    CAS  Google Scholar 

  12. V. M. Peshkova, N. V. Mel’chakova, β-Diketony (ser. “Analiticheskie reagenty”) β-Diketones (Ser. “Analytical Reagents”)], Moscow, Nauka, 1986, 200 pp. (in Russian).

    Google Scholar 

  13. 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 

  14. Kratkaya khimicheskaya entsiklopediya [Brief Chemical Encyclopedia], Moscow, 1995, V. I, IV, V (in Russian).

  15. Analysis of Silicones, Ed. A. L. Smith, Wiley-Interscience, New York-London, 41, 1974, part 2, 3.

    Google Scholar 

  16. 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 

  17. A.s. 1122748 SSSR; Byul. isobret. [Bull. Invent.], 1966 (in Russian).

  18. A. J. Gordon, R. A. Ford, The Chemist’s Comparion: A Handbook of Practical Data, Techiques, and Referens, Wiley, New York, 1973, 560 pp.

    Google Scholar 

  19. V. A. Igonin, O. I. Shchegolikhina, S. V. Lindeman, M. M. Levitsky, Yu. T. Struchkov, A. A. Zdanov, J. Organomet. Chem., 1992, 423, 351.

    Article  CAS  Google Scholar 

  20. B. Emmert, H. Gsottschneider, H. Stanger, Ber., 1936, 69, 1319.

    Google Scholar 

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Authors and Affiliations

  1. A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28 ul. Vavilova, 119991, Moscow, Russian Federation

    N. V. Sergienko, N. V. Cherkun, A. A. Korlyukov & B. G. Zavina

  2. N. S. Enikolopov Institute of Synthetic Polymeric Materials, Russian Academy of Sciences, 70 ul. Profsoyuznaya, 117393, Moscow, Russian Federation

    V. D. Myakushev

Authors
  1. N. V. Sergienko
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  2. N. V. Cherkun
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  3. V. D. Myakushev
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  4. A. A. Korlyukov
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  5. B. G. Zavina
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Correspondence to B. G. Zavina.

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Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1340–1346, July, 2010.

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Sergienko, N.V., Cherkun, N.V., Myakushev, V.D. et al. Reaction of the framework 3d-organometallosiloxanes with acetylacetone. Russ Chem Bull 59, 1369–1375 (2010). https://doi.org/10.1007/s11172-010-0248-3

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  • DOI: https://doi.org/10.1007/s11172-010-0248-3

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