The reactions of pyridinyl thioesters with triiron dodecacarbonyl: their novel diiron carbonyl complexes and mechanistic investigations.
The reactions of pyridinyl thioesters with triiron dodecacarbonyl: their novel diiron carbonyl complexes and mechanistic investigations.
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DOI：
10.1039/c2dt30798g
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发表时间：
2012-07
影响因子：
4
通讯作者：
Li Long;Zhiyin Xiao;Giuseppe Zampella;Zhenhong Wei;L. De Gioia;Xiaoming Liu
中科院分区：
文献类型：
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作者：
Li Long;Zhiyin Xiao;Giuseppe Zampella;Zhenhong Wei;L. De Gioia;Xiaoming Liu
Fe（3）（CO）（12）与吡啶硫酯配体PyCH（2）SCOCH（3）（L（1），Py =吡啶-2-基）反应生成配合物[Fe（2）（κ-COCH（3））（μ-SCH（2）Py）（CO）（5）]（1）（PyCH（2）S =吡啶-2-基甲硫醇盐）。当配合物1与PPh（3）反应时，得到一个单取代配合物[Fe（2）（κ-COCH（3））（μ-SCH（2）Py）（CO）（4）PPh（3）]（2）。通过与硫酯配体PyCH（2）SCOPy（L（2））反应，合成了三种新的双铁配合物[Fe（2）（κ-Py）（μ-SCH（2）Py）（CO）（5）]（3），[Fe（2）（κ-Py）（μ-SCH（2）Py）（CO）（5）]（4）和[Fe（2）（κ-Py）（μ-SCH（2）Py）（CO）（6）]（5）.配合物3和4是结构异构体。配合物5可以转化为配合物4，但没有观察到从配合物5到异构体3的转化。所有的五个配合物，充分其特征在于使用FTIR，NMR和其他技术。用X射线单晶衍射分析确定了它们的结构。配合物1、3、4和5的氧化形成涉及C-S和/或C-C键断裂。为了探测这些裂解的可能机制，进行DFT计算。从计算中，可行的反应途径，导致形成的所有分离的产品进行了划定。理论计算的结果也允许合理化的实验观察。
Reaction of Fe(3)(CO)(12) with pyridinyl thioester ligand PyCH(2)SCOCH(3) (L(1), Py = pyridin-2-yl) produced complex, [Fe(2)(κ-COCH(3))(μ-SCH(2)Py)(CO)(5)] (1) (PyCH(2)S = pyridin-2-ylmethanethiolate). When complex 1 reacted with PPh(3), a monosubstituted complex, [Fe(2)(κ-COCH(3))(μ-SCH(2)Py)(CO)(4)PPh(3)] (2), was derived. Reaction of the same precursor with analogous thioester ligand PyCH(2)SCOPy (L(2)) generated three novel diiron complexes, [Fe(2)(κ-Py)(μ-SCH(2)Py)(CO)(5)] (3), [Fe(2)(κ-Py)'(μ-SCH(2)Py)(CO)(5)] (4), and [Fe(2)(κ-Py)(μ-SCH(2)Py)(CO)(6)] (5). Complexes 3 and 4 are structural isomers. Complex 5 could be converted into complex 4 but the conversion from complex 5 to the isomer 3 was not observed. All the five complexes were fully characterised using FTIR, NMR, and other techniques. Their structures were determined using X-ray single crystal diffraction analysis. The oxidative formation of complexes 1, 3, 4, and 5 involved C-S and/or C-C bonds cleavages. To probe possible mechanisms for these cleavages, DFT calculations were performed. From the calculations, viable reaction pathways leading to the formation of all the isolated products were delineated. The results of the theoretic calculations also allowed rationalisation of the experimental observations.