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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

本文研究了硅、锗等重十四族元素组成的不饱和小环化合物的反应性。（1）环三硅烯的反应：环四硅烯鎓离子的合成与结构由取代的环三硅烯与[Et_3Si（C_6H_6）]^+·TPFPB^-在苯中反应，得到了对空气和水分敏感的黄色晶体环四硅烯鎓·TPFPB^-（TPFPB-=（C_6F_5）_4B^-）。X射线晶体学研究表明，环四硅烯鎓离子不仅是一个不与抗衡阴离子和溶剂分子相互作用的自由阳离子，而且是一个含硅的2π电子同芳香化合物。（2）环四硅烯鎓离子的反应性：环四硅烯自由基和环四硅烯鎓离子的合成与结构--环四硅烯鎓离子^-与大体积的三烷基硅钠通过单电子还原反应得到稳定的结晶化合物环四硅烯基， ...更多信息离子。晶体学分析表明，环四硅烯基自由基是一个自由的硅基，具有烯丙基型离域结构，没有任何分子间的相互作用。用Li、Na和KC_8在乙醚中还原环四硅烯鎓离子，得到环四硅烯鎓离子。环四硫烯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鎓离子，表明环四硅烯基阳离子、自由基和阴离子在烯丙基型硅π电子体系上表现出化学可逆的二电子氧化还原体系。（3）二硅锗烯与二价锗和锡的反应含Si=Si或Si=Ge双键的二硅锗烯衍生物与二氯锗烯-1，4二氧六环络合物，得到具有内环Ge=Ge双键的二硅双锗烯。二硅锗亚胺与二氯锡烯-1，4-二氧六环配合物反应也发生了同样的扩环反应，得到了含Ge=Sn双键的不饱和四元环化合物。