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，例如四面体，prismane和古巴，长期以来一直着迷化学家，因为高对称性引起的独特特性和美学吸引力。为了丰富14组元素化学的努力，硅和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外的新型物理和化学特性。但是，直到最近，这种综合被认为是不可能的。该项目的成功合成，隔离和表征，例如己二烷，己糖甲，六边形和octagermacubane。研究结果如下。1）通过X射线晶体学对octasilacubane和Octagermacubane的合成和表征。2）结构确​​定octasilacubane和octagermacubane的结构确定。3）合成和表征和己糖菌的合成和表征。 5）紫外线光谱和固态NMR光谱的物理特性。prismanes是苯，杜瓦苯，苯兹瓦列伦的价异构体。实际上，己二烷烷和六烷丙烷在低温下在溶液中辐照后，具有340-380 nm的光，在溶液中辐照后，提供了相应的露苯苯衍生物。

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。