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

基本信息

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

项目摘要

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

我们研究了硅、锗等重14族元素组成的不饱和小环化合物的反应性，本课题得到了以下结果：(1)环三硅烯的反应：环四硅鎓离子的合成与结构^tBu_2MeSi-的反应。苯中被[Et_3Si(C_6H_6)]^+·TPFPB^-取代的环三硅烯给出了对空气和湿气敏感的黄色晶体环四硅烯基鎓·TPFPB^-(TPFPB-=(C_6F_5)_4B^-)，X射线晶体学表明环四硅烯鎓离子不仅是一种游离阳离子，不与反阴离子和溶剂相互作用。分子，而是由硅 (2) 组成的 2π 电子同芳香族化合物环四硅鎓离子的反应性：环四硅烯基和环四硅烯基离子的合成和结构环四硅烯基离子^-与大的三烷基甲硅烷基钠通过单电子还原反应得到环四硅烯基自由基，为稳定的结晶化合物。晶体分析表明，环四硅烯基自由基是游离硅基自由基。具有烯丙基型离域结构，不含任何Li、Na和KC_8在乙醚中也实现了环四硅烯基离子的两个电子还原，得到环四硅烯基离子，环四硅烯基的逐步化学氧化成功地再生了环四硅烯基自由基和环四硅烯基离子，表明环四硅烯基阳离子、自由基、和阴离子显示化学可逆烯丙基型硅π电子体系上的双电子氧化还原体系(3)二硅勒吉烯与二价锗和锡的反应具有Si=Si或Si=Ge双键的二硅勒吉烯衍生物与二氯甲锗烷-1,4二恶烷络合物反应生成二硅勒二吉烯，其具有环内Ge=Ge双键，在disilagermirene与的反应中发生相同类型的扩环。二氯亚锡-1,4二恶烷络合物生成带有Ge=Sn双键的不饱和四元环化合物 Less