Polyhedral Silicon and Germanium Compounds

多面体硅和锗化合物

• 批准号: 07454159
• 负责人: SEKIGUCHI Akira
• 金额: $ 4.48万
• 依托单位: University of Tsukuba (1996-1997)Tohoku University (1995)
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 1995
• 资助国家: 日本
• 起止时间: 1995 至 1997
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-07454159/
• 关键词: organosilicon compound; organogermanium compound; cluster; polyhedral compound; prismane; cubane; heavy element; X-ray crystallography; 縮合反応; 官能基化; 光反応; デュワ-ベンゼン; 固体NMR; 芳香族性

Polyhedral carbon compounds such as tetrahedrane, prismane, and cubane have long fascinated chemists because of the unique properties and aesthetic appeal due to high symmetry. In an effort to enrich group 14 element chemisty, synthesis of the silicon and germanium analogues is a great challenge since it could lead to novel physical and chemical properties unexpected from the carbon compounds. However, such synthesis was thought to be impossible until recently. The successful syntheses, isolation, and characterization of polyhedral silicon and germanium compounds such as hexasilaprismane, hexagermaprismane, octasilacubane, and octagermacubane have been performed by this project. The research results are as follows.1) Synthesis and characterization of octasilacubane and octagermacubane.2) Structural determination of octasilacubane and octagermacubane by the X-ray crystallography.3) Synthesis and characterization of hexasilaprismane and hexagermaprismane.4) Stuctural determination of hexasilaprismane and hexagermaprismane by the X-ray crystallography.5) Physical properties by UV-Vis spectra and solid state NMR spectra.Prismanes are valence isomers of benzene, Dewar benzene, benzvalene. Indeed, the hexasilaprismane and hexagermaprismane afforded the corresponding Dewar benzene derivatives upon irradiation in solution at low temperature with light having wavelengths of 340-380 nm.

四面体、棱柱烷和立方烷等多面体碳化合物由于其高度对称性而具有独特的性质和美学吸引力，长期以来一直令化学家着迷。为了丰富第 14 族元素的化学性质，硅和锗类似物的合成是一个巨大的挑战，因为它可能会带来碳化合物意想不到的新物理和化学性质。然而，直到最近，这种合成还被认为是不可能的。该项目已成功合成、分离和表征了多面体硅和锗化合物，如六硅棱柱烷、六棱柱烷、八硅立方烷和八角立方烷。研究结果如下：1）八硅立方烷和八硅立方烷的合成与表征。2）X射线晶体学法测定八硅立方烷和八硅立方烷的结构。3）六硅棱柱烷和六硅棱柱烷的合成与表征。4）六硅棱柱烷和六硅棱柱烷的结构测定。通过 X 射线晶体学。5) 物理性质紫外-可见光谱和固态核磁共振光谱。棱柱石是苯、杜瓦苯、苯并瓦烯的化合价异构体。事实上，在低温溶液中用波长为340-380nm的光照射时，六硅棱柱烷和六硅棱柱烷提供相应的杜瓦苯衍生物。

项目成果

A.Sekiguchi, H.Yamazaki, C.Kabuto, H.Sakurai, and S.Nagase: "Cyclotrgermenes : A New Unsaturated Ring System" J.Am.Chem.Soc.117. 8025-8026 (1995)

A.Sekiguchi、H.Yamazaki、C.Kabuto、H.Sakurai 和 S.Nagase：“Cyclotrgermenes：一种新的不饱和环系统”J.Am.Chem.Soc.117。

Akira, Sekiguchi: "[Me(phMe_2Si)_2SiLi]and[Ph(Me_3Si)_2Li]:Preparation,Characterization,and Evidence for an Intramolecular Li-Ph Interaction." Angewandte Chemie International Edition in English. 36巻. 113-115 (1997)

Akira, Sekiguchi：“[Me(phMe_2Si)_2SiLi] 和 [Ph(Me_3Si)_2Li]：分子内 Li-Ph 相互作用的制备、表征和证据。Angewandte Chemie 国际版英文版第 36 卷。113-115（ 1997）

Akira Sekiguchi: "[Me(PhMe_2Si)_2SiLi] and [Ph(Me_3Si)_2Li] : Preparation,Characterization,and Evidence for an Intramolecular Li-Ph Interaction." Angewandte Chemie Internatinal Edition in English. 36巻. 113-115 (1997)

Akira Sekiguchi：“[Me(PhMe_2Si)_2SiLi] 和 [Ph(Me_3Si)_2Li]：分子内 Li-Ph 相互作用的制备、表征和证据。Angewandte Chemie 国际版英文版。” 1997）

A.Sekiguchi, M.Nanjo, C.Kabuto, and H.Sakurai: "Polysilane Dendrimers" J.Am.Chem.Soc.117. 4195-4196 (1995)

A.Sekiguchi、M.Nanjo、C.Kabuto 和 H.Sakurai：“聚硅烷树枝状聚合物”J.Am.Chem.Soc.117。

A.Sekiguchi: "Lithium and Sodium Complexes of a Tetrasilylethylene Dianion" Organometallics. 14. 1092-1094 (1995)

A.Sekiguchi：“四甲硅烷基乙烯二价阴离子的锂和钠配合物”有机金属。