A Synthetic Analogue of Rieske-Type [2Fe-2S] Clusters
A Synthetic Analogue of Rieske-Type [2Fe-2S] Clusters
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DOI：
10.1002/anie.200803418
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发表时间：
2008-01-01
影响因子：
16.6
通讯作者：
Meyer, Franc
中科院分区：
文献类型：
--
作者：
Ballmann, Joachim;Albers, Antonia;Meyer, Franc
1964年，在生物系统中发现了Rieske型[2Fe-2S]簇，并鉴定为[2Fe-2S]铁氧还蛋白的变体。[1]它们在结构上通过在[2Fe-2S]核心的不对称末端连接而不同于母体铁氧还蛋白，[2]由于这种独特的配位环境，Rieske型[2Fe-2S]簇合物的光谱(如EPR和穆斯堡尔)和功能特性(即电化学势)是不同的。[3]对合成模型络合物的研究为铁-硫协因子的性质和电子结构提供了有价值的见解。[4]虽然在过去的几十年里已经获得了几个具有全S或全N环境的仿生[2Fe-2S]簇合物，[4，5]到目前为止，还没有合成出模拟Rieske铁-硫蛋白特殊情况的不对称连接簇合物。[6]在这里，我们报道了第一个准确的Rieske型[2Fe-2S]簇合物的合成以及光谱和结晶学表征。
In 1964 Rieske type [2Fe-2S] clusters were discovered in biological systems and identified as variants of [2Fe-2S] ferredoxins.[1] Structurally they differ form the parent ferredoxins by an asymmetrical terminal ligation at the [2Fe-2S] core, with only one iron center coordinated by two cysteinyl thiolates and the other coordinated by two histidine nitrogen donors.[2] Spectroscopic (eg EPR and Mössbauer) and functional characteristics (namely the electrochemical potential) of Rieske type [2Fe-2S] clusters are distinct because of this unique coordination environment.[3] The investigation of synthetic model complexes has provided valuable insight into the properties and electronic structures of iron–sulfur cofactors.[4] While several biomimetic [2Fe-2S] clusters with all-S or all-N environments have been obtained over the last decades,[4, 5] no asymmetrically ligated cluster that emulates the particular situation of the Rieske iron–sulfur proteins could be synthesized to date.[6] Herein we report the synthesis as well as spectroscopic and crystallographic characterization of the first accurate synthetic model compound 4 for Rieske type [2Fe-2S] clusters.