Sequential oxidation of the cubane [4Fe--4S] cluster from [4Fe--4S](-) to [4Fe--4S](3+) in Fe(4)S(4)L(n)(-) complexes.
Sequential oxidation of the cubane [4Fe--4S] cluster from [4Fe--4S](-) to [4Fe--4S](3+) in Fe(4)S(4)L(n)(-) complexes.
复制标题
Fe(4)S(4)L(n)(-) 配合物中立方烷[4Fe--4S]簇从[4Fe--4S](-) 依次氧化为[4Fe--4S](3 )。
DOI：
10.1021/ja0498437
复制
发表时间：
2004
期刊：
影响因子：
--
通讯作者：
Wang,Lai-Sheng
中科院分区：
文献类型：
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作者：
Zhai,Hua-Jin;Yang,Xin;Fu,You-Jun;Wang,Xue-Bin;Wang,Lai-Sheng
用激光汽化固体Fe/S靶和电喷雾法制备Fe4Sn-(n= 4−6)团簇和Fe4S4Ln-（L = Cl, Br， I;n= 1−4）模拟物，并利用光电子能谱对其电子结构进行了探测。少数自旋Fe三维电子的低结合能特征与s衍生带明显不同。我们发现最简单的Fe4S4-cubane簇的电子结构可以用先前为[4Fe] cubane类似物开发的两层自旋耦合模型来描述。光电子数据显示，fe4s5和fe4s6中每增加一个S原子，就会从[4Fe−4S]立方核中去除两个自旋少的Fe 3d电子，而在fe4s4mn -配合物中，每增加一个卤素配体，就会从立方核中去除一个Fe 3d电子，这清楚地揭示了立方体在五个形式氧化态上的顺序氧化行为：[4Fe−4S]-→[4Fe−4S]0→[4Fe−4S]+→[4Fe−4S]2+→[4Fe−4S]3+。本研究显示了[4Fe−4S]立方烷的电子存储能力，有助于理解其电子结构，并进一步证明了立方烷作为结构单元和电子转移中心的鲁棒性。
Gaseous Fe4Sn-(n= 4−6) clusters and synthetic analogue complexes, Fe4S4Ln-(L = Cl, Br, I;n= 1−4), were produced by laser vaporization of a solid Fe/S target and electrospray from solution samples, respectively, and their electronic structures were probed by photoelectron spectroscopy. Low binding energy features derived from minority-spin Fe 3d electrons were clearly distinguished from S-derived bands. We showed that the electronic structure of the simplest Fe4S4-cubane cluster can be described by the two-layer spin-coupling model previously developed for the [4Fe] cubane analogues. The photoelectron data revealed that each extra S atom in Fe4S5-and Fe4S6-removes two minority-spin Fe 3d electrons from the [4Fe−4S] cubane core and each halogen ligand removes one Fe 3d electron from the cubane core in the Fe4S4Ln-complexes, clearly revealing a behavior of sequential oxidation of the cubane over five formal oxidation states: [4Fe−4S]-→ [4Fe−4S]0→ [4Fe−4S]+→ [4Fe−4S]2+→ [4Fe−4S]3+. The current work shows the electron-storage capability of the [4Fe−4S] cubane, contributes to the understanding of its electronic structure, and further demonstrates the robustness of the cubane as a structural unit and electron-transfer center.