多组份氧化还原体系的双二茂铁酰基硫脲及其铜配合物

Multicomponent Redox Systems Consisting of N-Ferrocenoyl-N'-ferrocenyl (ethylferrocene) Thiourea and Its Copper (Ⅱ) Complexes

利用不等价双二茂铁酰基硫脲多齿配体与氧化铜、醋酸铜反应合成了４个新型多核配合物，提出了配位模型。总结了配位前后ＩＲ、１ＨＮＭＲ的变化特征，并对它们的电化学性质进行了研究，发现２个配体中均含有２个不等价二茂铁，属于多组份氧化还原体系，但其与ＣｕＣｌ２、ＣｕＡｃ２形成多核配合物的电化学性质却呈现出平均化趋势，提出了相应的转化机理。

The two non-equivalent ferrocene fragments N-ferrocenoyl-N'-ferrocenyl thiourea (HL1) and N-ferrocenoyl-N'-ethylferrocene thiourea (HL2)are prepared by the addition of ferrocenoyl isothiocyanate with aminoferrocene and aminoethylferrocene respectively. The copper (Ⅱ) complexes of these ligands are isolated and have been characterized by elementary analyses and spectral (IR, 1H NMR) measurements. The redox behavior of the two ligands and their complexes is investigated by cyclic voltammeter.The legends(HL1,HL2) undergo two distinct and consecutive reversible oneelectron oxidation processes centred on the two non-equivalent ferrocene fragments, but in complex Cu(HL1)2Cl2, it is able to release two electrons at the same potentials.The two ferrocenyl groups change to equivalent ferrocene fragments.In the complex Cu (L2)Ac,it is still able to release two electrons at distinctly different potentials,Ep1, and Ep2.Ep1, and Ep2 values are chaning to close, such an approch is quite interesting. Some factors affecting the magnitude of the potential separation △E(△E=Ep2-Ep1) are envisaged.