Synthesis and characterisation of polymeric materials consisting of {Fe2(CO)5}-unit and their relevance to the diiron sub-unit of [FeFe]-hydrogenase.
Synthesis and characterisation of polymeric materials consisting of {Fe2(CO)5}-unit and their relevance to the diiron sub-unit of [FeFe]-hydrogenase.
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DOI：
10.1039/c0dt00687d
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发表时间：
2010-11
影响因子：
4
通讯作者：
Caixia Zhan;Xiufeng Wang;Zhenhong Wei;David J Evans;Xiang Ru;Xianghua Zeng;Xiaoming Liu
中科院分区：
文献类型：
--
作者：
Caixia Zhan;Xiufeng Wang;Zhenhong Wei;David J Evans;Xiang Ru;Xianghua Zeng;Xiaoming Liu
通过在二叠氮化合物和带有两个炔基的二铁模型配合物之间使用“点击”化学，制备了两种聚合二铁配合物（Poly-Py和Poly-Ph）。使用红外光谱、扫描电子显微镜（SEM）、透射电子显微镜（TEM）、热重分析（TGA）、穆斯堡尔谱和循环伏安法（由于Poly-Ph的不溶性，仅Poly-Py）研究了这两种聚合物复合物。为了探测两种聚合物复合物中二铁单元的配位模式，还使用单叠氮化物合成了两种对照复合物（3和4）。配合物3和4的特点是，后者进一步晶体学分析。结果表明，在两种配合物（3和4）和两种聚合物二铁配合物中，二铁单元中的两个铁原子之一与三唑N原子之一配位。研究结果表明，聚-Py和聚-Ph的形态和性能都受到二叠氮化合物有机部分的显著影响。与配合物3和4的质子化行为相比，Poly-Py表现出质子抗性。在电化学还原中，与络合物3和4相比，Poly-Py中的二铁单元的还原电位以及因此其在乙酸-DMF中的质子的催化还原电位偏移超过400 mV。很可能Poly-Py的聚合性质在酸性介质中为二铁单元提供了“保护性”环境和更正的还原电位。
By using "click" chemistry between a diazide and a diiron model complex armed with two alkynyl groups, two polymeric diiron complexes (Poly-Py and Poly-Ph) were prepared. The two polymeric complexes were investigated using infrared spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), thermal gravimetric analysis (TGA), Mössbauer spectroscopy, and cyclic voltammetry (Poly-Py only, due to the insolubility of Poly-Ph). To probe the coordinating mode of the diiron units in the two polymeric complexes, two control complexes (3 and 4) were also synthesised using a monoazide. Complexes 3 and 4 were well characterised and the latter was further crystallographically analysed. It turns out that in both complexes (3 and 4) and the two polymeric diiron complexes, one of the two iron atoms in the diiron unit coordinates with one of the triazole N atoms. Our results revealed that both morphologies and properties of Poly-Py and Poly-Ph are significantly affected by the organic moiety of the diazide. Compared to the protonating behaviour of the complexes 3 and 4, Poly-Py exhibited proton resistance. In electrochemical reduction, potentials for the reduction of the diiron units in Poly-Py and hence its catalytic reduction of proton in acetic acid-DMF shifted by over 400 mV compared to those for complexes 3 and 4. It is likely that the polymeric nature of Poly-Py offers the diiron units a "protective" environment in an acidic medium and more positive reduction potential.