摘要
合成了氯代硅宾化合物L(Cl)Si(1,L=PhC(Nt-Bu)2).1分别与HC≡CPPh_(2)、PhC≡CPPh_(2)和Ph_(2)PC≡CPPh_(2)反应,生成硅杂环丙烯L(Cl)Si(η^(2)-C_(2))(H)(PPh_(2))(4)、L(Cl)Si(η^(2)-C_(2))(Ph)(PPh_(2))(5)、L(Cl)Si(η^(2)-C_(2))(PPh_(2))2(6).1先后与Ph_(2)PLi和MesLi进行基团交换反应,得到膦基硅宾L(Ph_(2)P)Si(2)和芳基硅宾L(Mes)Si(3,Mes=2,4,6-Me3C6H2).2和3分别与Ph_(2)PC≡CPPh_(2)反应,生成硅杂环丙烯L(Ph_(2)P)Si(η^(2)-C_(2))(PPh_(2))2(7)和L(Mes)Si(η^(2)-C_(2))(PPh_(2))2(8).化合物4~8是一类含膦取代基的Si(η^(2)-C_(2))-三元环化合物,显示2个π电子的Hückel芳香性的稳定结构,是含硅杂环中张力最强的分子之一.
The chlorosilylene L(Cl)Si(1,L=PhC(Nt-Bu)2)was synthesized.Compound 1 reacted with HC≡CPPh_(2),PhC≡CPPh_(2),Ph_(2)PC≡CPPh_(2),producing silacyclopropenes L(Cl)Si(η^(2)-C_(2))(H)(PPh_(2))(4),L(Cl)Si(η^(2)-C_(2))(Ph)(PPh_(2))(5),and L(Cl)Si-(η^(2)-C_(2))(PPh_(2))2(6),respectively.Metathesis reactions using 1 with the respective Ph_(2)PLi and MesLi were further carried out,yielding phosphanyl and aryl silylenes L(Ph_(2)P)Si(2)and L(Mes)Si(3,Mes=2,4,6-Me3C6H2).Subsequently,the reactions of either 2 or 3 were able to occur with Ph_(2)PC≡CPPh_(2),affording silacyclopropenes L(Ph_(2)P)]Si(η^(2)-C_(2))(PPh_(2))2(7)and L(Mes)Si-(η^(2)-C_(2))(PPh_(2))2(8),respectively.Compounds 4~8 are the type of the Si(η2-C_(2))three-membered ring compounds,all containing the phosphanyl substituent and featuring the stable structure with 2πelectrons of the Hückel aromaticity.These compounds are considered as one of the most ring-strained molecules among the Si-containing heterocycles.
作者
陈艺林
岳佳怡
林依鸣
刘兵妮
戴闻
朱红平
Chen Yilin;Yue Jiayi;Lin Yiming;Liu Bingni;Dai Wen;Zhu Hongping(State Key Laboratory of Physical Chemistry of Solid Surfaces,College of Chemistry and Chemical Engineering,Xiamen University,Xiamen 361005;Jiangsu Nata Opto-electronic Material Co.,Ltd.,Soochow,Jiangsu 210046)
出处
《有机化学》
北大核心
2026年第1期128-134,共7页
Chinese Journal of Organic Chemistry
基金
国家自然科学基金(No.21972112)
福建省产学研(No.2021H6002)资助项目.
