Preparation of Novel Materials for Heterogeneous Catalysts from Oligosilsesquioxanes

具有立方核结构的含金属的低聚倍半硅氧烷从负载型催化剂或含金属的沸石的活性表面位点的定义明确的均相模型的观点引起了注意。在本工作中，合成了各种新型含金属的倍半硅氧烷，并将其转化为多孔氧化物或聚合物材料。因此，获得了以下结果。（1）新型乙烯基四族茂金属硅倍半氧烷的合成：合成了新型乙烯基二茂或茂金属硅倍半氧烷Cp_2M{[（vinyl）Me_2Si]（c-C_5 H_9）_7Si_7O_<12>}（Cp= CH_2，M=Zr，Hf），以及三甲基硅基二茂或茂金属硅倍半氧烷Cp_2Zr[（Me_3Si）（c-C_5 H_9）_7Si_7O_<12>]。还合成了含有二甲基乙氧基甲硅烷基的衍生物。（2）钛桥倍半硅氧烷和八（双（双）倍半硅氧烷）共低聚物的合成：在硅氢加成反应条件下，新型钛桥倍半硅氧烷Ti[（c-C_5 H_9）_7Si_7O_<12>（SiMe_2R）]_2（R=乙烯基，烯丙基）与八（双（双）倍半硅氧烷）反应得到低聚物。即使在低聚材料中，起始倍半硅氧烷的钛原子周围的局部结构也没有改变。（3）由镓桥硅倍半氧烷制备具有酸性中心的微孔Ga-Si-O材料：通过煅烧一种新型镓桥硅倍半氧烷[HNEt_3]^+{Ga[（Me_3Si）（c-C_5 H_9）_7Si_7O_ ]_2}，制备了具有酸性中心和均匀控制微孔的Ga-Si-O材料<12>。

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}.