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Synthesis and study of the structure of cage-like metallosiloxanes with pair combinations of 3d transition and alkaline earth metals

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Abstract

The selective replacement of Na ions in cage-like (Cu,Na) organosiloxanes in reactions with divalent metal halides was studied. The sandwich-like isomer [PhSiO2]6Cu4Na4[PhSiO2]6 forms the corresponding bimetallic complexes [PhSiO2]6Cu4M2[PhSiO2]6 (M = Cu, Zn, Mg, Sr, Ba) retaining a sandwich-like structure (in 60–90% yields) regardless of the metal ion size in MCl2. Under similar conditions, the reactions of the globular isomers [RSiO2]12Cu4Na4 (R = Ph, Me, Vin) with CuX2 (X = Cl or Br) afforded insoluble polymer products. The reaction in dioxane or THF in the presence of DMSO gave the crystalline globular-type metal complexes [RSiO2]12Cu4[CuX]4, in which Na ions are replaced by CuX groups. The compositions and structures of the synthesized metal complexes were studied by X-ray diffraction, elemental analysis, and destructive silylation combined with gel permeation chromatography and 1H NMR spectroscopy.

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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, A. A. Sochikhin, V. D. Myakushev, T. V. Strelkova & B. G. Zavin

Authors
  1. N. V. Sergienko
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  2. N. V. Cherkun
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  3. A. A. Korlyukov
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  4. A. A. Sochikhin
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  5. V. D. Myakushev
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  6. T. V. Strelkova
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  7. B. G. Zavin
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Correspondence to B. G. Zavin.

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Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1999–2006, September, 2013.

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Sergienko, N.V., Cherkun, N.V., Korlyukov, A.A. et al. Synthesis and study of the structure of cage-like metallosiloxanes with pair combinations of 3d transition and alkaline earth metals. Russ Chem Bull 62, 1999–2006 (2013). https://doi.org/10.1007/s11172-013-0290-z

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  • DOI: https://doi.org/10.1007/s11172-013-0290-z

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