Department of Chemistry, The University of Texas at Austin, Austin, TX, 78712, USA.
Angew Chem Int Ed Engl. 2021 Feb 15;60(7):3433-3437. doi: 10.1002/anie.202011517. Epub 2020 Dec 8.
The one-step syntheses, X-ray structures, and spectroscopic characterization of synthetic iron clusters, bearing either inorganic sulfides or thiolate with interstitial carbide motifs, are reported. Treatment of iron carbide carbonyl clusters [Fe (μ -C)(CO) ] (n=5,6; m=15,16; x=0,-2) with electrophilic sulfur sources (S Cl , S ) results in the formation of several μ -S dimers of clusters, and moreover, iron-sulfide-(sulfocarbide) clusters. The core sulfocarbide unit {C-S} serves as a structural model for a proposed intermediate in the radical S-adenosyl-L-methionine biogenesis of the M-cluster. Furthermore, the electrophilic sulfur strategy has been extended to provide the first ever thiolato-iron-carbide complex: an analogous reaction with toluylsulfenyl chloride affords the cluster [Fe (μ -C)(SC H )(CO) ] . The strategy described herein provides a breakthrough towards developing syntheses of biomimetic iron-sulfur-carbide clusters like FeMoco.
本文报道了具有无机硫化物或带有间隙碳化物配体的硫醇盐的合成铁簇的一步合成、X 射线结构和光谱特性。用亲电硫源（SCl2、S8）处理碳化铁羰基簇[Fe(μ-C)(CO)]（n=5,6；m=15,16；x=0，-2）会导致形成几个簇的μ-S 二聚体，并且会形成铁-硫化物-（硫代碳化）簇。核心硫代碳化单元{C-S}可用作提出的 M 簇中自由基 S-腺苷-L-蛋氨酸生物合成的中间产物的结构模型。此外，亲电硫策略已被扩展到提供首个硫醇盐-铁-碳化复合物：与对甲苯磺酰氯的类似反应得到了簇[Fe(μ-C)(SC6H5)(CO)]。本文所述的策略为开发类似 FeMoco 的仿生铁-硫-碳化簇的合成提供了突破。
