Single‐Step Sulfur Insertions into Iron Carbide Carbonyl Clusters: Unlocking the Synthetic Door to FeMoco Analogues
Single‐Step Sulfur Insertions into Iron Carbide Carbonyl Clusters: Unlocking the Synthetic Door to FeMoco Analogues
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DOI：
10.1002/ange.202011517
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发表时间：
2020-10
影响因子：
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通讯作者：
C. Joseph;Caitlyn R. Cobb;Michael J. Rose
中科院分区：
文献类型：
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作者：
C. Joseph;Caitlyn R. Cobb;Michael J. Rose
我们报告的一步合成，X-射线结构和光谱表征的合成铁簇轴承无机硫化物或硫醇盐与间隙碳化物图案。用亲电硫源（S2 Cl 2，S8）处理历史上的碳化铁-羰基簇合物[Fen（μ n-C）（CO）m ] x（n = 5，6; m = 15，16; x = 0，-2），生成了几个μ 4 -S '簇合物二聚体'（1和2），此外还生成了硫化铁-（硫碳化物）簇合物3和4 . 3和4中的核心“碳化物”基序是硫碳化物单元{C-S} 4-，其作为M-簇的自由基SAM生物成因中所提出的中间体的结构模型。此外，“亲电硫”策略已被扩展以提供有史以来第一个硫醇合铁碳化物络合物：与甲苯磺酰氯（tolS-Cl）的类似反应提供簇合物[Fe 5（μ 5 -C）（SC 7 H 7）（CO）13 ] -（5）。本文所述的“亲电硫供体”策略为开发仿生铁-硫-碳化物簇如FeMoco的逻辑合成提供了突破。
We report the one-step syntheses, X-ray structures, and spectroscopic characterization of synthetic iron clusters bearing inorganic sulfides or thiolate with interstitial carbide motifs. Treatment of historical iron-carbide-carbonyl clusters [Fe n ( μ n -C)(CO) m ] x ( n = 5,6; m = 15,16; x = 0,-2) with electrophilic sulfur sources (S 2 Cl 2 , S 8 ) results in the formation of several μ 4 -S 'dimers of clusters' ( 1 and 2 ), and moreover the iron-sulfide-(sulfocarbide) clusters 3 and 4 . The core 'carbide' motif in 3 and 4 is the sulfocarbide unit {C-S} 4- , which serves as a structural model for the proposed intermediate in the radical-SAM 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 (tolS-Cl) affords the cluster [Fe 5 ( μ 5 -C)(SC 7 H 7 )(CO) 13 ] - ( 5 ). The 'electrophilic sulfur donor' strategy described herein provides a breakthrough towards developing logical syntheses of biomimetic iron-sulfur-carbide clusters like FeMoco.