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

• 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
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-11166250/
• 关键词: steric protection; disilyne; dilithiosilane; dilithiogermane; silacyclopropabenzene; germacyclopropabenzene; 9-silaanthracene; 2-germanaphthalene; 速度論的安定化; 2-ゲルマナフタレン; 芳香族化合物; ジリチオスタンナン; ゲルマニウム

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，我们正在研究的合成和分离的新的，高活性物种稳定的空间位阻保护和阐明他们的性质，利用光谱，X射线晶体学分析，和理论计算。虽然我们还没有合成硅-硅三键化合物，这是该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族元素的新型应变环化合物，金属环丙苯，和2）含有较重的14族元素的新型杂芳族化合物，9-硅蒽和2-锗萘，三[双（三甲基甲硅烷基）甲基]苯基（Tbt），其是有用的反应性化合物。1）硫代金属烷[Tbt（Dip）Mli_2：M = Si，Ge]与邻二溴苯反应生成相应的金属环丙苯[Tbt（Dip）MC_6H_4：M = Si，Ge]（1）。1的X-射线结构分析表明，金属环丙苯环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基团成功地合成并分离了第一个稳定的9-硅杂蒽和2-锗杂萘。光谱数据。X射线结构分析和理论计算表明，9-硅蒽和2-锗萘环是完全平面的，它们是芳香族化合物。此外，还确定了9-硅蒽和2-锗萘分别具有Si=C和Ge=C双键化合物的反应活性。

项目成果

Norihiro Tokitoh: "Synthesis. Structures, and Reactivities of Novel Silacyclic Systems : the First Stable Silabcnzene and Silacyclopropabenzene"Phosphorus, Sulfur and Silicon. 168-169. 31-40 (2001)

Norihiro Tokitoh：“新型硅环系统的合成、结构和反应性：第一个稳定的硅环苯和硅环丙苯”磷、硫和硅。

Norihiro Tokitoh: "Recent Advances in the Chemistry of Group 14-Group 16 Double Bond Compounds"Adv.Organomet.Chem.. 47. 121-166 (2001)

Norihiro Tokitoh：“第 14 族-第 16 族双键化合物化学的最新进展”Adv.Organomet.Chem.. 47. 121-166 (2001)

Keiji Wakita: "Synthesis and Properties of an Overcrowded Silabenzene Stable at Ambient Temperature"Angew.Chem.Int.Ed.. 39. 634-636 (2000)

Keiji Wakita：“环境温度下稳定的过度拥挤的硅苯苯的合成和性能”Angew.Chem.Int.Ed.. 39. 634-636 (2000)

Norihiro Tokitoh: "Formation of Antimony-Sulfur Double-Bond Compounds and Their Trapping with Nitrile Oxides"Heteroatom Chem.. 12. 244-249 (2001)

Norihiro Tokitoh：“锑硫双键化合物的形成及其与腈氧化物的捕获”Heteroatom Chem.. 12. 244-249 (2001)

Norihiro Tokitoh: "Synthesis and Characterization of an Extremely Hindered Tetraaryl-substituted Digermene and Its Unique State and in Solution"Polyhedron. (in press).

Norihiro Tokitoh：“极度受阻四芳基取代的二锗烯及其独特状态和溶液的合成和表征”多面体。