New Aspect of Tetrahedrane : Synthesis and Properties of Highly Strained σ-π Condugated Molecules

四面体的新面貌：高应变σ-π共轭分子的合成与性能

• 批准号: 21750033
• 负责人: NAKAMOTO Masaaki
• 金额: $ 3万
• 依托单位: University of Tsukuba
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Young Scientists (B)
• 财政年份: 2009
• 资助国家: 日本
• 起止时间: 2009 至 2010
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-21750033/
• 关键词: 高周期典型元素化合物; ケイ素化合物; 高歪み分子; σ-π共役; 高歪み化合物; テトラヘドラン; シクロブタジエン; 原子価異性化

Tetrahedrane is a hydrocarbon with highly strained carbon-carbon σ bonds. Because of the extremely strained skeleton, the increase in the energy level of C-C σ-bond orbitals results in the σ-π conjugation between tetrahedrane σ-frame with adjacent π-orbital system. We have investigated the synthesis, structural analysis and properties of perfluoroaryl substituted tetrahedranes. Up to now, there is also no report of stable heteroatom such as sulfur substituted tetrahedranes. We report the synthesis, structure and properties of phenylthio tetrahedranes which was prepared by the nucleophilic substitution of diphenyldisulfide and tetrahedranyllithim. Our tetrahedranes were fully characterized by NMR and X-ray crystallography. On the measurement of UV-vis spectrum of perfluoroaryl substituted tetrahedranes, a significant bathochromic shift relative to the non-substituted perfluorobenzene was observed. It indicate the extended σ-π conjugation of tetrahedrane σ-frame and perfluoroaryl π-system.

四面体是具有高应变的碳碳σ键的烃。由于骨骼极为紧张，C-Cσ-键轨道的能级的增加导致四面体与相邻π-轨道系统之间的σ-π共轭。我们已经研究了全氟化替代的四面体的合成，结构分析和特性。到目前为止，还没有关于稳定杂原子的报道，例如硫取代的四面体。我们报告了由核植物酶和四面体四氢酶制备的苯基硫硫非类药物的合成，结构和特性。我们的四面体充分表征了NMR和X射线晶体学。在测量全氟亚替代的四面体的UV-VIS光谱上，观察到相对于非取代的全氟苯的显着bathochromic移位。它表明四面体σ框和perfluoroarylπ系统的扩展σ-π结合。

项目成果

Photoisomerization of Perfluoroaryltetrahedranes to Perfluoroarylcyclobutadienes

• DOI: 10.1021/ja208354x
• 发表时间: 2011-10-19
• 期刊: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
• 影响因子: 15
• 作者: Inagaki, Yusuke;Nakamoto, Masaaki;Sekiguchi, Akira
• 通讯作者: Sekiguchi, Akira