高自旋[Fe=S]配合物夺取氢原子。
Hydrogen atom abstraction by a high spin [Fe=S] complex.
作者信息
Valdez-Moreira Juan A, Wannipurage Duleeka C, Pink Maren, Carta Veronica, Moënne-Loccoz Pierre, Telser Joshua, Smith Jeremy M
机构信息
Department of Chemistry, Indiana University, Bloomington, IN 47405, USA.
Department of Chemical Physiology and Biochemistry, School of Medicine, Oregon Health & Science University, Portland, OR 97239, USA.
出版信息
Chem. 2023 Sep 14;9(9):2601-2609. doi: 10.1016/j.chempr.2023.05.007. Epub 2023 May 31.
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] fragment. Here, we report the synthesis and characterization of a terminal iron sulfido complex. Despite its high spin ( = 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 an = 3/2 iron(III) disulfido (S ) 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.
铁硫簇对众多生物过程至关重要；然而，对于这些簇的基本单元，即[Fe=S]片段，人们了解甚少。在此，我们报告了一种末端硫铁配合物的合成与表征。尽管其基态具有高自旋（S = 5/2），但结构、光谱和计算表征为铁硫多重键特征提供了证据。有趣的是，该配合物与额外的硫反应生成一个S = 3/2的二硫铁（III）（S₂²⁻）配合物。初步研究表明，硫铁配合物与二氢蒽反应生成一个氢硫铁（II）配合物，类似于铁氧配合物的反应活性。相比之下，二硫配合物则不发生反应。这些结果为硫化铁单元的性质提供了重要见解。
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