炔桥联不对称苯基取代双二茂铁衍生物的设计合成和电化学性质
Designed Syntheses and Electrochemistry Properties of Alkynyl-Bridged Asymmetric Phenyl Substituted Biferrocenyl Derivatives
作者单位E-mail
张骁勇 内蒙古工业大学化工学院, 呼和浩特 010051
包头师范学院化学学院, 包头 014030 
 
韩利民 内蒙古工业大学化工学院, 呼和浩特 010051  
高媛媛 内蒙古工业大学化工学院, 呼和浩特 010051  
贾慧劼 内蒙古工业大学化工学院, 呼和浩特 010051  
索全伶 内蒙古工业大学化工学院, 呼和浩特 010051 szj010062@163.com 
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'-COCH35),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125、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12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(Epa(Fc'-H)=0.658 V,Epa(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(ΔE1=0.236 V;ΔE2=0.170 V;ΔE3=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。
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
基金项目: 国家自然科学基金(No.21062011,21266019)资助项目。
Abstract: 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…π interactions 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 the ΔE values of corresponding compounds were significantly enhanced while two different groups Fc' and Fc are bridged into alkynyl linkage.
Keywords: pentaphenylferrocenylacetylene  alkynyl-bridged phenyl substituted biferrocenyl  designed synthesis  electrochemical property  crystal structure
投稿时间:2017-11-20 修订日期:2018-03-09
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张骁勇,韩利民,高媛媛,贾慧劼,索全伶.炔桥联不对称苯基取代双二茂铁衍生物的设计合成和电化学性质[J].无机化学学报,2018,34(5):864-873.
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