| 不对称双二茂铁脲衍生物的合成、表征及电子传递性质 |
| Synthesis, Characterization and Electron Transfer Properties of Unsymmetrical Diferrocenyl Urine Derivative |
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| 摘要: 以二茂铁为原料,通过多步反应,首先合成了对称的桥联双二茂铁脲(5),再将其与胱胺反应,合成了一种新的不对称桥联双二茂铁脲衍生物MeOOC-Fc-NH-CO-NH-Fc-CO-NH-(CH2)2-S-S-(CH2)2-NH2(7)(Fc:二茂铁)。对目标产物进行了红外、紫外、1HNMR和MS表征;由于目标化合物7含有不对称的二茂铁脲这一特殊结构,采用循环伏安(CV)方法对化合物7的电子迁移特性进行了研究。结果表明2个二茂铁之间通过脲键传递电子,从而使2个二茂铁基团可以分别被氧化,它们的氧化电位差ΔEo"为181mV,它们之间的稳定常数Kc为1145。相对于对称的二茂铁脲(5)(ΔEo"=140mV,Kc=207),这种不对称结构分子中2个二茂铁之间电子间的相互作用增强。 |
| 关键词: 不对称双二茂铁脲 合成 电子迁移 混价化合物 |
| 基金项目: 国家自然科学基金资助项目(No.20676153) |
| Abstract: The symmetrical bridged diferrocenyl urine derivative MeOOC-Fc-NH-CO-NH-Fc-COOMe(5) was formed during the synthesis of ferrocene derivatives.This symmetrical compound(5)was then reacted with cystamine,unsymmetrical ureylene bridged diferrocene derivative MeOOC-Fc-NH-CO-NH-Fc-CO-NH-(CH2)2-S-S-(CH2)2-NH2(7) was obtained.The identity of the titled compound was confirmed by IR,UV,1H NMR and MS spectra.Due to its unique unsymmetrical structure,the electron transfer properties were investigated by cyclic voltammetry.The experimental results show that electronic coupling between the two Fc groups through the ureylene bridge results in both Fc groups being individually oxidizable.The existence of intermolecular electronic communication is discussed.The separation potentials between two ferrocene groups is ΔEo"=181 mV,and the comproportionation constant Kc=1145,while for the symmetrical compound of urine bridged diferrocene,its ΔEo" and Kc are 140 mV and 207,respectively.The extent of the electronic interaction between the two redox sites of title compound is higher than that of symmetrical compound. |
| Keywords: unsymmetrical ureylene bridged diferrocene synthesis electron transfer mixed-valence molecule |
| 投稿时间：2007-10-10 修订日期：2007-12-24 |
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| 李春兰,魏传晚,王蓓,刘又年.不对称双二茂铁脲衍生物的合成、表征及电子传递性质[J].无机化学学报,2008,24(3):375-380. |
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