摘要
以四苯基环戊二烯酮为起始原料,经过八步连续反应,成功地合成了3个炔桥联不对称五苯基取代双二茂铁衍生物Fc′-C≡C-Fc(1)、Fc′-C≡C-C≡C-Fc(2)和Fc′-C≡C-C≡C-Fc′(3)(Fc′=五苯基二茂铁基,Fc=二茂铁基)。在设计合成双二茂铁衍生物的过程中,首先经过4步反应,制备出已知化合物Fc′-H(4),再连续进行3步反应,分别得到3个中间化合物Fc′-COCH_3(5),Fc′-CCl=CHCHO(6)和Fc′-C≡CH(7),最后利用偶联反应,得到目标化合物1~3。利用X射线单晶衍射和循环伏安法,测定了化合物1、2和5、7的晶体结构,研究了化合物1~7的电化学性质。研究结果表明,分子的C-H…π键相互作用和空间位阻是导致化合物1和2分子中Fc′和Fc基空间排布取向不同的主要原因。当二茂铁的一个环戊二烯环上引入5个苯取代基时,铁中心的氧化还原电位将升高(E_p^a(Fc′-H)=0.658 V,E_p^a(Fc-H)=0.511 V)。与已知化合物Fc-C≡C-Fc(ΔE=0.215 V)和Fc-C≡C-C≡C-Fc(ΔE=0.134 V)相比,化合物1~3的氧化电位差值(ΔE)均有不同程度地提高(ΔE_1=0.236 V;ΔE_2=0.170 V;ΔE_3=0.146 V)。将1与Fc-C≡C-Fc,2与Fc-C≡C-C≡C-Fc和3进行比较发现,当炔桥两端连接不同的基团Fc′和Fc时,其氧化电位差值(ΔE)将明显提高。
Three asymmetric alkynyl-bridged pentaphenyl substituted biferrocenyl derivatives Fc′-C≡C-Fc(1),Fc′-C≡C-C≡C-Fc(2)and Fc′-C≡C-C≡C-Fc′(3)(Fc′=pentaphenylferrocenyl,Fc=ferrocenyl)were successfully synthesized by eight successive reaction steps using tetraphenylcyclopentadienone as starting material.In the process gaining compounds 1~3,three intermediate products Fc′-COCH3(5),Fc′-CCl=CHCHO(6)and Fc′-C≡CH(7)were also obtained by three-step continuous reaction using known compound Fc′H(4)prepared by four-step reaction.The crystal structures of compounds 1,2 and 5,7 were determined by X-ray single crystal diffraction technique,and the electrochemical properties of compounds 1~7 were studied by cyclic voltammetry.The results show the C-H…πinteractions and the steric hindrance result in the different space orientations of Fc′and Fc units in the crystals of 1 and 2.The redox potential of the iron center is increased(Epa(Fc′-H)=0.658 V,Epa(Fc-H)=0.511 V)while five phenyls are introduced into a five-membered ring of ferrocenyl unit.Comparing with known compounds Fc-C≡C-Fc and Fc-C≡C-C≡C-Fc(ΔEFc-C≡C-Fc=0.215 V,ΔEFc-C≡C-C≡C-Fc=0.134 V),the oxidation potential differences(ΔE)of 1~3 are all elevated(ΔE1=0.236 V;ΔE2=0.170 V;ΔE3=0.146 V).In comparison with 1 and Fc-C≡C-Fc,with 2 and Fc-C≡C-C≡C-Fc and 3,we discover theΔE values of corresponding compounds were significantly enhanced while two different groups Fc′and Fc are bridged into alkynyl linkage.CCDC:1542614,1;1542615,2;1546347,5;1546346,7.
作者
张骁勇
韩利民
高媛媛
贾慧劼
索全伶
ZHANG Xiao-Yong;HAN Li-Min;GAO Yuan-Yuan;JIA Hui-Jie;SUO Quan-Ling(Chemical Engineering College,Inner Mongolia University of Technology,Hohhot 010051,China;Department of Chemistry,Baotou Teachers′College,Baotou,Inner Mongolia 014030,China)
出处
《无机化学学报》
SCIE
CAS
CSCD
北大核心
2018年第5期864-873,共10页
Chinese Journal of Inorganic Chemistry
基金
国家自然科学基金(No.21062011
21266019)资助项目
关键词
五苯基二茂铁乙炔
炔桥联苯基取代双二茂铁基
设计合成
电化学性质
晶体结构
pentaphenylferrocenylacetylene
alkynyl-bridged phenyl substituted biferrocenyl
designed synthesis
electrochemical property
crystal structure
