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

基于空间保护概念的新物种合成方法的发展

基本信息

批准号：
11166250
负责人：
TOKITOH Norihiro
金额：
$ 18.24万
依托单位：
Kyoto University (2000-2001)Kyushu University (1999)
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research on Priority Areas (A)
财政年份：
1999
资助国家：
日本
起止时间：
1999 至 2001
项目状态：
已结题

项目摘要

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.

在这个项目中，我们通过利用光谱，X射线晶体学分析和理论计算来研究新型，高反应性物种的合成和分离。 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-甘苯二乙烯，Tris [bis（三甲基甲硅烷基）甲基]苯基（TBT）组，这是有用的反应化合物。 s通过利用各种高反应性化合物的2,4,6稳定。1）二硫代（dip）mli_2：m = si，ge]与o-二溴苯苯的反应，从1的X射线结构分析表明，金属丙烷丙苯环的结构参数几乎与父级金属乙丙烷丙烯烯的计算参数一致。金属丙二苯甲酸的环完全平均，1的应变小于环甲苯的应力。2）我们成功地通过利用TBT组的优势来成功地合成和分离了第一个稳定的9-硅烷和2-甘帕乙烯。光谱数据。 X射线结构分析以及理论计算表明，9-二兰氨基氨基烯和2-甘苯顿甲烯环是完全平面的，它们是芳族化合物。此外，阐明了9-硅烷性和2-甘酸乙烯的反应性分别为Si = C和GE = C = C双键化合物。