Chlorine K-Edge X-ray Absorption Spectroscopy as a Probe of Chlorine-Manganese Bonding: Model Systems with Relevance to the Oxygen Evolving Complex in Photosystem II †
Chlorine K-Edge X-ray Absorption Spectroscopy as a Probe of Chlorine-Manganese Bonding: Model Systems with Relevance to the Oxygen Evolving Complex in Photosystem II †
复制标题
氯 K 边 X 射线吸收光谱作为氯-锰键合探针：与光系统 II 中的放氧复合物相关的模型系统 †
DOI：
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发表时间：
1997
期刊：
影响因子：
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通讯作者：
M. Klein
中科院分区：
文献类型：
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作者：
A. Rompel;J. Andrews;R. M. Cinco;M. Wemple;G. Christou;N. A. Law;V. Pecoraro;K. Sauer;V. Yachandra;M. Klein
对于一系列Mn−Cl配合物，已经测量了氯K边X射线吸收光谱（XAS）以探测氯锰键合。结果表明，在一系列的单核（单锰）化合物与氯共价结合到锰，前边缘功能的强度增加的顺序MnII < MnIII < MnIV。对于一系列扭曲的立方烷配合物（含4锰）与桥接和终端氯配体，三个前边缘功能。随着化合物中包含更多末端氯，最低能量处的边缘前峰强度增加。边缘光谱中的这些功能的起源中描述的对称性和配位场分裂预期的Mn络合物。这里研究的Mn模型系统具有潜在的应用，在光系统II（PSII），其中直接的结构证据的卤化物结合位点上的Mn簇在一个或多个S-状态的角周期的氧释放复合物（OEC）将是有益的。
For a series of Mn−Cl coordination complexes the chlorine K-edge X-ray absorption spectra (XAS) have been measured to probe chloride−manganese bonding. Results show that in a series of mononuclear (single Mn) compounds with Cl covalently bound to Mn, the intensity of the pre-edge feature increases in the order MnII < MnIII < MnIV. For a series of distorted cubane complexes (containing 4 Mn) with bridging and terminal Cl ligands, three pre-edge features are seen. The pre-edge peak at lowest energy increases in intensity as more terminal Cl are included in the compounds. The origin of these features in the edge spectra is described in terms of the symmetry and ligand field splittings expected for the Mn complexes. The Mn model systems studied here have potential application to the oxygen evolving complex (OEC) in Photosystem II (PSII), where direct structural evidence for a halide binding site on the Mn cluster in one or more S-states of the Kok cycle would be informative.