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.

多面体碳化合物，如四面体烷，棱镜烷和立方烷长期以来吸引了化学家，因为其独特的性质和美学吸引力，由于高度对称性。在丰富第14族元素化学的努力中，硅和锗类似物的合成是一个巨大的挑战，因为它可能导致碳化合物意想不到的新的物理和化学性质。然而，这种合成直到最近才被认为是不可能的。本项目成功地合成、分离和表征了多面体硅锗化合物，如六硅癸烷、六锗癸烷、八硅立方烷和八锗立方烷。本论文的主要研究结果如下：1）八硅立方烷和八角立方烷的合成与表征; 2）八硅立方烷和八角立方烷的X-射线晶体学结构测定; 3）六硅癸烷和六硅癸烷的合成与表征; 4）六硅癸烷和六硅癸烷的X-射线晶体学结构测定; 5）紫外-可见光谱物理性质测定。棱镜烷是苯、杜瓦苯、苯并瓦烯的价态同分异构体。实际上，在低温下用波长为340-380 nm的光照射溶液时，六硅癸烷和六锗癸烷得到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）

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。

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）

Keisuke Ebata: "Intramolecular Oligomerization of Disilalkylene {-Me_2Si(CH_2)_nSiMe_<2->} Bridged Cyclic Triacetylenes." Chemistry Letters. 12号. 1053-1054 (1996)

Keisuke Ebata：“二硅亚烷基 {-Me_2Si(CH_2)_nSiMe_<2->} 桥环三乙炔的分子内齐聚。”12. 1053-1054 (1996)