Preparation of Novel Materials for Heterogeneous Catalysts from Oligosilsesquioxanes

具有立方核结构的含金属倍半硅氧烷从负载催化剂或含金属沸石的活性表面中心的定义明确的、均一的模型的角度引起了人们的注意。本工作合成了多种新型的含金属倍半硅氧烷，并将其转化为多孔氧化物或聚合物材料。(1)新型含乙烯基茂金属倍半硅氧烷的合成：合成了新型含四茂金属的乙烯基倍半硅氧烷(Cp_2M{[(vinyl)Me_2Si](c-C_5H_9)_7Si_7O_&lt；12&gt；}(Cp=cyclopentadienyl，M=Zr，Hf)及其三甲基硅基衍生物Cp_2Zr[(Me_3Si)(c-C_5H_9)_7Si_7O&lt；12&gt；]。(2)钛桥倍半硅氧烷与倍半硅氧烷共低聚物的合成：新的含烯基钛桥倍半硅氧烷(Ti[(c-C_5H_9)_7Si_7O_&lt；12&gt；(SiMe_2R)]_2(R=vinyl，烯丙基)与倍半硅氧烷在硅氢化反应条件下反应得到低聚物。(3)由倍半硅氧烷制备具有酸性中心的微孔材料：通过焙烧一种新的倍半硅氧烷[HNEt_3]^{Ga[(Me_3Si)(c-C_5H_9)_7Si_7O&lt；12&gt；]_2}制备了具有酸性中心和均匀可控微孔的Ga-Si-O材料。

Metal-containing oligosilsesquioxanes with cubic core structures have attracted attention from the viewpoint of well-defined, homogeneous models for the active surface sites of the supported catalysts or metal-containing zeolites. In the present work, synthesis of various novel metal-containing silsesquioxanes and transformation of them into porous oxides or polymeric materials have been performed. Accordingly followillg results were acquired.(1)Synthesis of Novel Group 4 Metallocene-containing Silsesquioxanes with a Vinyl Group :Novel zirconocene or hafnocene-containing silsesquioxanes with vinyl group Cp_2M{[(vinyl)Me_2Si](c-C_5H_9)_7Si_7O_<12>}(Cp=cyclopentadienyl, M=Zr, Hf)were synthesized, as well as a derivative with a trimethylsilyl group Cp_2Zr[(Me_3Si)(c-C_5H_9)_7Si_7O_<12>]. A derivative containing a dimethylethoxysilyl group was also synthesized.(2)Synthesis of Cooligomers of Titanium-Bridged Silsesquioxanes and Octakis(hydridosilsesquioxane) :New titanium-bridged silsesquioxanes having olefinic groups, Ti[(c-C_5H_9)_7Si_7O_<12>(SiMe_2R)]_2(R=vinyl, allyl), react with octakis(hydridosilsesquioxane)under hydrosilylation reaction conditions to give oligomeric materials. The local structure around the titanium atoms of the starting silsesquioxanes is unchanged even in the oligomeric materials.(3)Preparation of Microporous Ga-Si-O Materials with Acidic Sites from a Gallium-Bridged Silsesquioxane :Ga-Si-O materials with acidic sites and uniformly-controlled micropores have been prepared by the calcination of a new gallium-bridged silsesquioxane[HNEt_3]^+{Ga[(Me_3Si)(c-C_5H_9)_7Si_7O_<12>]_2}.