Theoretical study on the structure–reactivity relationships of acetylacetone–Fe catalyst modified by ionic compound in C–H activation reaction

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• 作者：Xingbang Hu ; Yong Sun ; Jianyong Mao ; Haoran Li
• 关键词：Structure– ; reactivity relationship ; C– ; H activation ; Acetylacetone– ; Fe ; Anion ; Cation ; Methane ; Ionic compound
• 刊名：Journal of Catalysis
• 出版年：2010
• 出版时间：15 June 2010
• 年：2010
• 卷：272
• 期：2
• 页码：320-332
• 全文大小：1432 K

文摘

The reactivity of acetylacetone–Fe can be tuned by introducing an ionic compound (IC) group onto the ligand in the investigation into 41 different catalysts. This IC-modification alters the spin density carried by Fe/O atoms (SD_Fe/SD_O), the charge carried by O atom (Q_O), and the isotropic fermi contact couplings of O atom (IFCC_O) in the FeO part, thereby influencing the reactivity of the catalyst. The IC-modification that increases the SD_O, Q_O, and IFCC_O or decreases the SD_Fe can make the catalyst more powerful. The order of the correlation between the structure parameters and reactivity is SD_O > Q_O > SD_Fe ≈ IFCC_O > LUMO_C–HOMO_R  LUMO_C–HOMO_C ≈ Q_Fe. Changing the anion of the IC-catalyst is a more effective way to increase the reactivity compared with changing the cation, and the order is . Long distance between the IC part and the catalytic active center however weakens the influence induced by the IC-modification. These structure–reactivity relationships are expected to be used in catalyst design.