Electronic structure and intrinsic redox properties of [2Fe-2S]+ clusters with tri- and tetracoordinate iron sites
Electronic structure and intrinsic redox properties of [2Fe-2S]+ clusters with tri- and tetracoordinate iron sites
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DOI：
10.1021/ic048559d
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发表时间：
2005-03-07
影响因子：
4.6
通讯作者：
Wang, LS
中科院分区：
文献类型：
--
作者：
Fu, YJ;Niu, SQ;Wang, LS
利用潜在的双齿配体（-SC₂H₄NH₂），我们通过[4Fe - 4S](2+)配合物的裂解制备了具有不同配位几何结构的[2Fe - 2S](+)物种。尽管这些配体在立方烷配合物中是单齿的，但由于三配位铁位点的高反应性，在[2Fe]裂解产物中通过自组装观察到了单齿和双齿配合物。利用光电子能谱和密度泛函计算对[2Fe]物种的电子结构进行了探究。研究发现，四配位显著降低了[2Fe]配合物的电子结合能，从而提高了[2Fe - 2S](+)簇的还原能力。
Using potentially bidentate ligands (-SC2H4NH2), we produced [2Fe-2S](+) species of different coordination geometries by fission of [4Fe-4S](2+) complexes. Even though the ligands are monodenlate in the cubane complexes, both mono- and bidentate complexes were observed in the [2Fe] fission products through self-assembly because of the high reactivity of the tricoordinate iron sites. The electronic structure of the [2Fe] species was probed using photoelectron spectroscopy and density functional calculations. It was found that tetracoordination significantly decreases the electron binding energies of the [2Fe] complexes, thus increasing the reducing capability of the [2Fe-2S](+) clusters.