Hydrogen atom abstraction by a high-spin [FeIII=S] complex
Hydrogen atom abstraction by a high-spin [FeIII=S] complex
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DOI：
10.1016/j.chempr.2023.05.007
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发表时间：
2023-09-14
期刊：
影响因子：
23.5
通讯作者：
Smith，Jeremy M.
中科院分区：
文献类型：
--
作者：
Valdez-Moreira，Juan A.;Wannipurage，Duleeka C.;Smith，Jeremy M.
铁硫簇合物对许多生物过程至关重要;然而，人们对这些簇合物的基本单元，即[Fe=S]n+片段知之甚少。在这里，我们报告的终端铁硫化物复合物的合成和表征。尽管其高自旋（S= 5/2）的基态，结构，光谱和计算表征提供了铁硫多重键字符的证据。有趣的是，该配合物与额外的硫反应，得到S = 3/2二硫代铁（III）（S22-）配合物。初步的研究表明，硫配合物与二氢蒽反应，得到一个铁（II）的氢硫配合物，类似于铁氧配合物的反应性。相反，与二硫键络合物没有反应。这些结果提供了重要的洞察硫化铁单元的性质。
Iron-sulfur clusters are critical to a plethora of biological processes; however, little is known about the elementary unit of these clusters, namely, the [Fe=S]n+fragment. Here, we report the synthesis and characterization of a terminal iron sulfido complex. Despite its high-spin (S= 5/2) ground state, structural, spectroscopic, and computational characterization provide evidence for iron sulfur multiple bond character. Intriguingly, the complex reacts with additional sulfur to afford anS= 3/2 iron(III) disulfido (S22−) complex. Preliminary studies reveal that the sulfido complex reacts with dihydroanthracene to afford an iron(II) hydrosulfido complex, akin to the reactivity of iron oxo complexes. By contrast, there is no reaction with the disulfido complex. These results provide important insight into the nature of the iron sulfide unit.