- Synthesis and characterization of alkylgermasesquioxanes
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Alkyl (chloro)ethoxygermanes, RGe(OEt)nCl3-n (R = i-Pr, n = 0; R = t-Bu, n =0-3; R = cyclo-C6H11, n = 0) were hydrolyzed with aqueous NaOH in xylene at 130-140 °C to give cage hexakis(alkylgermasesquioxane)s, (RGe)6O9. These structures of cage (RGe)6O9 were fully confirmed by spectroscopic and X-ray diffraction methods. t-Butyldichloro(ethoxy)germane, t-BuGe(OEt)Cl2, was carefully treated with water at 5 °C for 3 h to afford cis, trans -1,3,5-tri-t -butyl-1,3,5-trichlorocyclotrigermoxane, (t-BuClGeO)3. Hydrolysis of (t-BuClGeO)3 at 5 °C for additional 33 h gave a tricyclic anti-form ladder prepared by hydrolysis of t-butyl(chloro)diethoxygermane, t-BuGe(OEt)2Cl, at 5 °C for 6 h, and its structure was determined by spectroscopic and X-ray diffraction analysis. The tricyclic ladder germoxane reacted with aqueous NaOH in xylene at 1300-140 °C for 3 h to afford hexakis(t-butylgermasesquioxane), (t-BuGe)6O9. The formation mechanism of the germasesquioxane, (t-BuGe)6O9 from t-butyl(chloro)ethoxygermanes, t-BuGe(OEt)nCl3-n (n = 0-3) is also discussed.
- Nanjo, Masato,Sasage, Takaomi,Mochida, Kunio
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- Methods for Preparing Germanium Dihalides
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Germanium dichloride and dibromide and their complexes with dioxane were prepared in a reasonable yield by reduction of germanium tetrachloride and tetrabromide with zinc in the presence of dioxane.
- Shcherbinin,Shvedov,Pavlov,Komalenkova,Chernyshev
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p. 1013 - 1016
(2007/10/03)
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- ZUR CHEMIE VON t-BUTYLGERMANIUM-HALOGENIDEN UND -CHALKOGENIDEN
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Upon reaction with an excess of t-C4H9Li GeCl4 gives 2 (I) and with 2 equivalents of t-C4H9Li it gives (t-C4H9)2GeCl2 (II) together with rearranged and condensated products (III, IV, V) and polycondensates.The reaction with 3 molar equivalents of t-C4H9Li gives predominantly (t-C4H9)3GeCl (VI) with a minor amount of I.Also (t-C4H9)2GeH2 (VII) could be isolated.In the presence of triethylamine from the reaction of II with H2S, (t-C4H9)2Ge(SH)2 (VIII) is obtained, which readily condenses to give cyclotetra-t-butyl-1,3-dithia-2,4-digermane (IX).IX can be also obtained in high yields from the reaction of I and sulfur, and from II and KHS in the presence of 18-crown-6, with cyclotetra-t-butyl-1,2,4-trithia-3,5-digermane (X) as a byproduct.X is the main product in the reaction of II and H2S in the presence of imidazole.From I and selenium or tellurium the corresponding 4-membered ring compounds XI and XII are obtained, with the 5-membered ring compound XIII as a byproduct of the reaction with selenium.The compounds are characterized spectroscopically (MS, 1H-NMR, and partly IR) and for those which have been separated in a pure state also by analyses.An X-ray structure determination has been performed for IX.
- Wojnowska, Maria,Noltemeyer, Mathias,Fuellgrabe, Hans-Juergen,Meller, Anton
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p. 229 - 238
(2007/10/02)
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