Development of Synthetic Methods for Novel Species on the bases of Concept of Steric Protection

在这个项目中，我们正在研究空间保护稳定的新型高活性物种的合成和分离，并利用光谱分析、X射线晶体分析和理论计算来阐明它们的性质。虽然我们还没有合成硅-硅三键化合物，这是本项目最重要的目标分子之一，但我们已经成功地合成了1)含有较重的14族元素金属环丙苯的新型张紧环化合物，以及2)含有较重的14族元素的新型杂芳烃化合物9-硅并2-锗并三[双(三甲基硅基)甲基]苯基(TBT)，这是一种有用的反应性化合物。S利用了各种高活性化合物的2，4，6-稳定作用。1)二锂硫杂多烯[TBT(Dip)MLI_2：m=Si，Ge]与邻二溴苯反应，得到相应的金属环丙苯[TBT(Dip)MC_6H_4：M=Si，Ge](1)。1的X-射线结构分析表明，金属环丙苯的结构参数与母体金属环丙苯的计算参数基本一致。2)利用TBT基团，我们成功地合成了第一个稳定的9-氮杂菲和2-锗基萘。光谱数据。X-射线结构分析和理论计算表明，9-硅杂环和2-锗萘环是完全平面的，是芳香族化合物。此外，还证实了9-硅杂菲和2-锗并萘的反应活性分别为Si=C和Ge=C双键化合物。

In this project, we arc studying the synthesis and isolation of novel, highly reactive species stabilized by steric protection and the elucidation of their properties by taking advantage of the spectrometry, X-ray crystallographic analysis, and theoretical calculations. Although we have not synthesized a silicon-silicon triple-bond compound, which is one of the most important target molecules of this project, we have succeeded in the synthesis of 1) novel, strained ring compounds containing a heavier group 14 element, metallacyclopropabenzenes, and 2) new type of heteraaromatic compounds containing a heavier group 14 element, 9-silaanthracene and 2-germanaphthalene, tris [bis (trimethylsilyl) methyl] phenyl (Tbt) group, which is useful reactive compounds. S by for taking advantage of 2,4,6-stabilization of various highly reactive compounds.1) Reactions of dilithiometallanes [Tbt(Dip)Mli_2 : M = Si, Ge] with o-dibromobenzene gave the corresponding metallacyclopropabenzenes [Tbt(Dip)MC_6H_4 : M = Si, Ge] (1). The X-ray structural analysis of 1 indicated that the structural parameters of the metallacyclopropabenzene rings are nearly consistent with the calculated parameters for the parent metallacyclopropabenzenes. The metallacyclopropabenzene rings are completely planar and the strain of 1 is smaller than that of cyclopolrpabenzenes.2) We succeeded in the synthesis and isolation of the first stable 9-silaanthracene and 2-germanaphthalene by taking advantage of Tbt group. The spectroscopic data. X-ray structural analyzes, and theoretical calculations indicated that the 9-silaanthracene and 2-germanaphthalene rings are completely planar, and that they are aromatic compounds. In addition, it was elucidated that 9-silaanthracene and 2-germanaphthalene showed the reactivities as Si=C and Ge=C double-bond compounds, respectively.