新型二茂铁茚基化合物的设计、合成及电化学性质研究  

Study on Design,Synthesis and Electrochemical Properties of Novel Ferrocenyl Indenyl Compounds

作　　者：贾慧劼[1] 师家乐 高媛媛[1] 王亚琦[1] 索全伶[1] JIA Hui-jie;SHI Jia-le;GAO Yuan-yuan;WANG Ya-qi;SUO Quan-ling(Chemical Engineering College, Inner Mongolia University of Technology, Hohhot 010051, China)

机构地区：[1]内蒙古工业大学化工学院,内蒙古呼和浩特010051

出　　处：《合成化学》2021年第6期468-475,共8页Chinese Journal of Synthetic Chemistry

基　　金：国家自然科学基金资助项目(21266019)。

摘　　要：利用Sonogashira偶联反应,以1,1′-二碘二茂铁(I-C_(5)H_(4)FeC5H_(4)-I),1,1′-二碘联二茂铁(I-C_(5)H_(4)FeC5H_(4)-C_(5)H_(4)FeC5H_(4)-I)和2-乙炔茚(Ind-C≡CH)为原料,设计合成了6种新型二茂铁茚基化合物I-C_(5)H_(4)FeC5H_(4)-C≡C-Ind(1,Ind为茚基),Ind-C≡C-C_(5)H_(4)FeC5H_(4)-C≡C-Ind(2),I-C_(5)H_(4)FeC5H_(4)-C_(5)H_(4)FeC5H_(4)-C≡C-Ind(3),Ind-C≡C-C_(5)H_(4)FeC5H_(4)-C_(5)H_(4)FeC5H_(4)-C≡C-Ind(4),C5H5FeC5H4-C≡C-C_(5)H_(4)FeC5H_(4)-C≡C-Ind(5),Fc-C≡C-C_(5)H_(4)FeC5H_(4)-C_(5)H_(4)FeC5H_(4)-C≡C-Ind(6,Fc为二茂铁基),其结构经^(1)H NMR,^(13)C NMR,MS(ESI)和X-射线单晶衍射表征,其中化合物1~3的晶体结构为首次报道。采用循环伏安法研究了化合物1~6的电化学性质。结果表明:取代基对调控二茂铁茚基衍生物二茂铁基之间的电子交互作用显著。单二茂铁茚基衍生物1和2中分别引入不对称和对称的共轭取代基团后,二茂铁基的氧化电位值升高。联二茂铁茚基衍生物3和4二茂铁基之间的电子交互作用基本不受取代基的影响。在乙炔桥相连接的取代二茂铁茚基衍生物5中,受金属-金属间距增加的影响,两个二茂铁基之间的电子交互作用减弱。不对称地引入二茂铁乙炔和乙炔茚取代基后,联二茂铁茚基衍生物6的两个二茂铁基之间的电子交互作用明显减弱。Six novel ferrocenyl indenyl compounds I-C_(5)H_(4)FeC5H_(4)-C≡C-Ind(1,Ind=indenyl),Ind-C≡C-C_(5)H_(4)FeC5H_(4)-C≡C-Ind(2),I-C_(5)H_(4)FeC5H_(4)-C_(5)H_(4)FeC5H_(4)-C≡C-Ind(3),Ind-C≡C-C_(5)H_(4)FeC5H_(4)-C_(5)H_(4)FeC5H_(4)-C≡C-Ind(4),C5H5FeC5H4-C≡C-C_(5)H_(4)FeC5H_(4)-C≡C-Ind(5)and Fc-C≡C-C_(5)H_(4)FeC5H_(4)-C_(5)H_(4)FeC5H_(4)-C≡C-Ind(6,Fc=ferrocenyl)were designed and synthesized by Sonogashira coupling reaction of 1,1′-diiodineferrocene(I-C_(5)H_(4)FeC5H_(4)-I),1,1″-diiodinediferrocene and 2-acetylene indene.Their structures were characterized by ^(1)H NMR,^(13)C NMR,MS(ESI)and X-ray single crystal diffraction.The crystal structures of new compounds 1~3 were determined for the first time by X-ray single crystal diffraction technique.The electrochemical properties of compounds 1~6 were studied by cyclic voltammetry(CV)method.The results show the substituents of ferrocenyl indenyl derivatives significantly affect the regulation of electron interaction between ferrocenyl groups.The oxidation potential of the single ferrocenyl indenyl derivatives 1 and 2 with the symmetric and asymmetric conjugated substituent is increased.The electron communication between two ferrocenyl units of diferrocenyl derivatives 3 and 4 is not basically affected by their substituent groups.The electron communication between two ferrocenyl groups bridged by ethynyl unit in substituted ferrocenyl indenyl derivatives 5 is also weakened by the effect of distance increase between two metals.The electron communication between two ferrocenyl pairs of compound 6 with asymmetric conjugated ferrocenyl ethynyl and indenyl ethynyl substituents is obviously weakened.

关 键 词：茚基配体 偶联反应 二茂铁基衍生物 合成 晶体结构 电化学性质 

分 类 号：O614.8[理学—无机化学] O621.3[理学—化学]