Studies on the Synthesis, Structures, Properties and Functions of Aromatic Compounds Containing Heavier Group 14 Elements

迄今为止，还没有稳定的、中性的含重14族元素的杂芳族化合物，它们的结构和性质尚未被揭示。本课题利用有效的空间位阻保护基，合成了新型的含重14族元素的杂芳环化合物2，4，6-三[双（三甲基硅基）甲基]苯基（Tbt）和2，6-双[双（三甲基硅基）甲基]-4-[三（三甲基硅基）甲基]苯基（Bbt），并对其结构和性质进行了研究。在此基础上，我们利用Tbt和Bbt基团成功地合成和分离了第一个稳定的硅杂苯、1-硅杂萘、2-硅杂萘、9-硅杂蒽、9-硅杂菲、锗杂苯、2-锗杂萘和9-锗杂蒽晶体。通过X射线结构分析、核磁共振、紫外/维斯光谱和拉曼光谱数据以及理论计算，表明这些化合物都是芳香族化合物以及相应的碳类似物。结果表明，这些化合物与水、甲醇等发生了1，2-或1，4-加成反应，并与第6族金属形成了η^6-金属杂苯芳烃配合物（Cr，Mo，（W）我们认为，本项目所获得的新知识为含重基杂芳族化合物的化学研究奠定了基础14个元素。我们期望在这些结果的基础上揭示含重14族元素的杂芳族化合物的新性质和功能，显示潜在的应用价值。这类化学不仅可用于新型功能化合物的合成，而且可用于新型催化。

There has been no stable, neutral heteraaromatic compounds containing heavier group 14 elements, and their structures and properties have not been revealed yet. In this project, we studied on the synthesis of new type of heteraaromatic compounds containing a heavier group 14 element by taking advantage of effective steric protection group, 2,4,6-tris[bis(trimethylsilyl)methyl]phenyl (Tbt) and 2,6-bis[bis(trimethylsilyl)methyl]-4-[tris(trimethylsilyl)methyl]phenyl (Bbt) and elucidated their sturctures and properties. Based on these results, we revealed the aromaticity of these compounds.We succeeded in the synthesis and isolation of the first stable silabenzene, 1-silanaphthalene, 2-silanaphthalene, 9-silaanthracene, 9-silaphenanthrene, germabenzene, 2-germanaphthalene, and 9-germaanthracene as stable crystals by taking advantage of Tbt and Bbt groups. The X-ray structural analyses, spectral data on NMR, UV/vis, and Raman spectroscopy, and theoretical calculations indicated that all these compounds are aromatic compounds as well as the corresponding carbon analogues. It was elucidated that these compounds underwent ready 1,2-or 1,4-addition towards the Si=C or Ge=C double-bond with H_2O, MeOH, and so on. Interestingly, the sila-and germabenzene were found to form the η^6-metallabenzene arene complexes with group 6 metals (Cr,Mo,and W).We think that the new knowledge obtained in this project lays the foundations of the chemistry of heteraaromatic compounds containing heavier group 14 elements. We expect that novel properties and functions of heteraaromatic compounds containing heavier group 14 elements will be revealed on the basis of these results, showing the potential applicability. Such chemistry will be applied to not only the synthesis of novel functional compounds but also the novel catalysis.