| 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 |
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| 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'-COCH3（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（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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