【摘要】 使用价格低廉且储量丰富的铁基催化剂实现了环氧化物的开环反应,其中Fe（BF₄）₂·6H₂O表现出最优的催化效果.研究发现,该反应能以高区域选择性得到醛产物,当以1,4-二氧六环为溶剂,添加0.01 mmol Fe（BF₄）₂·6H₂O催化1,2-环氧辛烷开环反应时,辛醛收率高达98%,选择性为99%.该反应体系适用于多种烷基和芳基取代的环氧化物.循环实验结果表明, Fe（BF4）2·6H2O可在保持良好催化活性的前提下重复使用3次,在第4次反应时催化剂开始出现显著失活的现象.采用傅里叶变换红外光谱（FTIR）、 X射线衍射（XRD）、 X射线荧光光谱（XRF）以及热重分析（TGA）等手段对催化剂进行表征发现,其失活原因在于反应过程中B和F元素的流失对催化剂的结构及配位性能造成了影响.这进一步证明了催化剂的作用机制并揭示了失活机理,并为该类催化剂在均相体系中的高效应用提供了理论依据.更多还原

【Abstract】 In this work, the ring-opening of epoxides was realized using cheap and abundant iron-based catalysts, in which Fe（BF₄）₂·6H₂O showed the best catalytic effects. The results showed that aldehyde could be obtained with high selectivity in this reaction. The ring-opening of 1,2-epoxyoctane in the presence of 0.01 mmol Fe（BF₄）₂·6H₂O was applied with 1,4-dioxane as solvent, the yield of octanal was up to 98% with a selectivity of 99%. Gratifyingly, this catalytic system was suitable for a variety of alkyl-and aryl-substituted epoxides. Furthermore, the recycling experiments showed that Fe（BF4）2·6H2O could maintain excellent catalytic activities when reused for three times, but then deactivated dramatically at the fourth recycle. In order to further understand the reason of catalyst deactivation, Fourier Transform infrared spectoscopy（FTIR）, X-ray diffraction（XRD）, X-ray fluorescence（XRF） and thermal gravimetric analysis（TGA） were used to analyze the catalyst. It was found that the reason of deactivation was the loss of B and F elements during the reactions, which affected the structure of the catalyst, as well as the coordination ability with epoxides. These findings further proved the mechanism of this reaction and revealed the reason of deactivation, and also provided a theoretical basis for the efficient application of this type of catalysts in homogeneous systems.更多还原