Biomimetic [2Fe-2S] clusters with extensively delocalized mixed-valence iron centers.
Biomimetic [2Fe-2S] clusters with extensively delocalized mixed-valence iron centers.
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DOI：
10.1002/anie.201506788
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发表时间：
2015-10
影响因子：
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通讯作者：
Shenglai Yao;F. Meier;Nils Lindenmaier;R. Rudolph;B. Blom;Mario Adelhardt;Jörg Sutter;S. Mebs;M. Haumann;K. Meyer;M. Kaupp;M. Driess
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文献类型：
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作者：
Shenglai Yao;F. Meier;Nils Lindenmaier;R. Rudolph;B. Blom;Mario Adelhardt;Jörg Sutter;S. Mebs;M. Haumann;K. Meyer;M. Kaupp;M. Driess
一系列完整的仿生[2Fe-2S]簇合物[（L（Dep）Fe）2（μ-S）2 ]（3）L（Dep）=CH[CMeN（2，6-Et2 C6 H3）]2）、[（L（Dep）Fe）2（μ-S）2 K]（4）、[（L（Dep）Fe）2（μ-S）2 ][Bu4 N]（5，Bu=n-butyl）和[（L（Dep）Fe）2（μ-S）2K2]（6）。[（L（Dep）Fe）2（μ-H）2 ]（2）与单质硫反应生成全铁[2Fe-2S]簇合物3。用1摩尔当量的元素钾对3进行化学还原，得到接触离子对K（+）[2Fe-2S]（-）（4）作为一维配位聚合物，其又与[Bu 4 N]Cl反应，得到单独的离子对[Bu 4 N]（+）[2Fe-2S]（-）（5）。用钾进一步还原4会使超还原的全铁[2Fe-2S]簇6变黑。值得注意的是，配合物4和5是[2Fe-2S]簇合物，具有广泛的离域Fe（2+）Fe（3+）对，由（57）Fe穆斯堡尔谱，X射线吸收和发射光谱（XAS，XES）和根据DFT计算证明。
A complete series of biomimetic [2Fe-2S] clusters, [(L(Dep) Fe)2 (μ-S)2 ] (3, L(Dep) =CH[CMeN(2,6-Et2 C6 H3 )]2 ), [(L(Dep) Fe)2 (μ-S)2 K] (4), [(L(Dep) Fe)2 (μ-S)2 ][Bu4 N] (5, Bu=n-butyl), and [(L(Dep) Fe)2 (μ-S)2 K2 ] (6), could be synthesized and characterized. The all-ferric [2Fe-2S] cluster 3 is readily accessible through the reaction of [(L(Dep) Fe)2 (μ-H)2 ] (2) with elemental sulfur. The chemical reduction of 3 with one molar equivalent of elemental potassium affords the contact ion pair K(+) [2Fe-2S](-) (4) as a one-dimensional coordination polymer, which in turn reacts with [Bu4 N]Cl to afford the separate ion pair [Bu4 N](+) [2Fe-2S](-) (5). Further reduction of 4 with potassium furnishes the super-reduced all-ferrous [2Fe-2S] cluster 6. Remarkably, complexes 4 and 5 are [2Fe-2S] clusters with extensively delocalized Fe(2+) Fe(3+) pairs as evidenced by (57) Fe Mössbauer, X-ray absorption and emission spectroscopy (XAS, XES) and in accordance with DFT calculations.