Syntheses, Properties, and Reactivities of Unsaturated Ring Compounds Consisting of Silicon and Germanium

硅、锗不饱和环化合物的合成、性质及反应活性

• 批准号: 13440185
• 负责人: SEKIGUCHI Akira
• 金额: $ 9.47万
• 依托单位: University of Tsukuba
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 2001
• 资助国家: 日本
• 起止时间: 2001 至 2003
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-13440185/
• 关键词: Heavier Group 1-4 Element; Organosilicon Compound; Organogermanium Compound; Unsaturated Small Ring Compound; Radical Species of Heavier Group 14 Element; Cation Species of Heavier Group 14 Element; Anion Species of Heavier Group 14 Element; Multip

We have studied the reactivity of unsaturated small ring compound consisting of heavier Group 14 Elements such as silicon and germanium. The following results have been obtained in this project(1)The Reaction of Cyclotrisilene : Synthesis and Structure of Cyclotetrasilenylium IonThe reaction of ^tBu_2MeSi-substituted cyclotrisilene with [Et_3Si(C_6H_6)]^+・TPFPB^-in benzene gave cyclotetrasilenylium・TPFPB^-(TPFPB-=(C_6F_5)_4B^-) as air-and moisture-sensitive yellow crystals. X-ray crystallography revealed that the cyclotetrasilenylium ion is not only a free cation without the Interaction with counter anion and solvent molecules, but a 2π-electron homoaromatic compound consisting of silicon(2)Reactivities of Cyclotetrasilenylium Ion : Synthesis and Structure of Cyclotetrasilenyl Radical and Cyclotetrasilenylide IonThe reaction of the Cyclotetrasilenylium ion^-with bulky trialkylsilylsodium afforded cyclotetrasilenyl radical as a stable crystalline compound through the one electron reduct … More ion. The crystallographic analysis reveals that the cyclotetrasilenyl radical is a free silyl radical, having an allyl type delocalized structure, without any intermolecular interaction. Two electron reduction of the Cyclotetrasilenylium ion was also achieved by Li, Na, and KC_8 in diethyl ether to give cyclotetrasilenide ion. Stepwise chemical oxidation of cyclotetraslienid successfully regenerates the cyclotetrasilenyl radical and the Cyclotetrasilenylium Ion, indicating that cyclotetrasilenyl cation, radical, and anion show chemically reversible two electron redox system on the allyl type silicon π-electron system(3)The Reaction of Disilagermirene with Divalent Species of Germanium and TinDisilagermirene derivatives with Si=Si or Si=Ge double bond react with dichlorogermylene-1,4 dioxane complex to give disiladigermetene, which have an endocyclic Ge=Ge double bond. The same type ring expansion took place in the reaction of disilagermirenes with dichlorostannylene-1,4 dioxane complex to afford unsaturated four membered ring compound bearing Ge=Sn double bond Less

我们研究了不饱和小环化合物的反应性，这些环化合物包括较重的组14个元素，例如硅和锗。在该项目中获得了以下结果（1）环丙硅烷的反应：环二苯基离子的合成和结构，^TBU_2Mesi-溶解的环烷基与[et_3si（C_6H_6）]环乙烯基苯基・ tpfpb^ - （tpfpb- =（c_6f_5）_4b^ - ）作为空气和水分敏感的黄色晶体。 X射线晶体学表明，环苯基苯基离子不仅是自由阳离子，而没有与反阴离子和溶液分子相互作用的情况环乙烯基离子与笨重的试验kylsodium提供了环甲基苯基自由基，作为一种稳定的晶体化合物，通过一种电子还原……更多。晶体学分析表明，环甲基苯基自由基是一个游离的平甲硅烷基自由基，具有烯丙基类型的离域结构，而没有任何分子间相互作用。 Two electron reduction of the Cyclotetrasilenyl ion Stepwise chemical oxidation of cyclotetraslienid successfully regenerates the cyclotetraslienyl radical and the Cyclotetraslienyl Ion, indicating that cyclotetraslienyl cation, radical, and anion show chemically reversible two electron redox system on the allyl type silicon π-electron system(3)The Reaction of脱脂式葡萄球菌和丁香苯甲酸衍生物具有si = si或si = ge双键与二氯甲苯1,4二氧烷复合物的反应，产生二甲基二甲苯，具有二甲基二甲苯，具有二甲基二甘油，具有二甲基二糖，具有二甲基二甘油，具有内吞ge = ge = ge dee double键。同一类型的环膨胀发生在disilagermirene与二氯苯乙烯-1,4二恶烷复合物的反应中，可提供不饱和的四个成员环复合轴承GE = SN双键

项目成果

Vladimir Ya.Lee, Masaaki Ichinohe, Akira Sekiguchi: "2,4-Disila-l-germatricyclo[2.1.0.0^<2.5>]pentane : A New Type Cage Compound of Group 14 Elements with an Extremely Long Ge-C Bridge Bond and an "Umbrella"-Type Configuration of a Ge Atom"J.Am.Chem.Soc..

Vladimir Ya.Lee、Masaaki Ichinohe、Akira Sekiguchi：“2,4-Disila-l-germatricyclo[2.1.0.0^<2.5>]戊烷：具有极长 Ge-C 桥键的新型 14 族元素笼状化合物

Akira Sekiguchi: "Bis(tri-tert-butylsilyl)silylene : Triplet Ground State Silylene"Journal of the American Chemical Society. 125・17. 4962-4963 (2003)

Akira Sekiguchi：“双（三叔丁基甲硅烷基）亚甲硅基：三重基态硅基”美国化学会杂志 125・17 4962-4963（2003 年）。

Kazuyuki Ishii, Nagao Kobayashi, sukasa Matsuo, Masanobu Tanaka, Akira Sekiguchi: "Observation of the Predicted Negative Faraday A MCD Term in a Cyclobutadiene Dianion"J.Am.Chem.Soc.. 123. 5356-5357 (2001)

Kazuyuki Ishii、Nagao Kobayashi、sukasa Matsuo、Masanobu Tanaka、Akira Sekiguchi：“环丁二烯二价离子中预测的负法拉第 A MCD 项的观察”J.Am.Chem.Soc.. 123. 5356-5357 (2001)

Akira Sekiguchi: "The First Halogen-Substituted Cyclotrigermenes : A Unique Halogen Walk over the Three Membered Ring Skeleton and Facial Stereoselectivity in the Diels-Alder Reaction"Journal of the American Chemical Society. 124・7. 1158-1159 (2002)

Akira Sekiguchi：“第一个卤素取代的环三甲烯：Diels-Alder 反应中独特的卤素行走三元环骨架和面立体选择性”，美国化学会杂志 124・7。

Kazuyuki Ishii: "Observation of the Predicted Negative Faraday A MCD Term in a Cyclobutadiene Dianion"Journal of the American Chemical Society. 123・22. 5356-5357 (2001)

Kazuyuki Ishii：“环丁二烯二价离子中预测的负法拉第 A MCD 项的观察”美国化学会杂志 123・22（2001 年）。