铁(Ⅲ)的氮杂环配合物的合成、结构及对环己烷氧化的催化性能

doi:10.3724/SP.J.1095.2014.30439

摘要/Abstract

摘要： 制备了铁氮杂环配合物[Fe(H2L)2]·(CH3COO)2·(OH)·H2O(H2L=2,6-二(5-甲基-1H-吡唑-3-基)吡啶)，通过元素分析、X射线粉末衍射和X射线单晶结构分析等技术手段表征了它的结构。将其用于液相环己烷的催化氧化，系统研究了H2O2用量、HNO3用量、水量、反应时间和温度等对中间活性物种环己基过氧化氢(C6H11OOH) 的生成和分解的影响，探讨了反应机理。结果表明，H2O2是氧化环己烷为C6H11OOH的主要氧化剂；硝酸对此过程没有氧化作用，但能大幅度提高C6H11OOH分解成环己醇(酮)的分解速率。 H2O会抑制中间物种C6H11OOH的生成和分解，而降低催化剂的比活性。在不同反应阶段，C6H11OOH和环己醇(酮)的生成速率不同。升温能促进C6H11OOH的分解速率，而有利于环己醇(酮)的生成。

关键词: 铁配合物, 二(甲基-1H-吡唑基)吡啶, 环己烷氧化, 环己基过氧化氢, 反应机理

Abstract: One novel iron complex, [Fe(H2L)2]·(CH3COO)2·(OH)·H2O(H2L=2,6-di-(5-methyl-1H-pyrazol-3-yl)pyridine) with N-donor ligand 2,6-di-(5-methyl-1H-pyrazol-3-yl)pyridine, was synthesized and characterized by elemental analysis, powder X-ray diffraction(PXRD) and single-crystal X-ray diffraction. In addition, the catalytic activity of the complex to cyclohexane oxidation was examined. The effects of various reaction factors such as the amount of H2O2, HNO3 and water, reaction time, as well as the temperature on the formation and decomposition of cyclohexylhydroperoxide, and the yield of C6H10O and C6H11OH were evaluated. The mechanism of oxidation reaction was also discussed. It shows that H2O2 is the main oxidant for the oxidation of cyclohexane to C6H11OOH catalyzed by the titled Fe complex; HNO3 has no oxidizing effect on this process, but can accelerate the formation and decomposition rates of C6H11OOH. Water has an inhibition effect on the catalytic activity, thereby lowering the formation and decomposition rates of C6H11OOH. The formation rates of C6H11OOH and C6H10O(C6H11OH) are different at different reaction stages. Higher temperature can promote the decomposition of C6H11OOH, which benefits the formation of C6H10O and C6H11OH.

Key words: iron complex,di-(methy-1H-pyrazol-yl)pyridine, cyclohexane oxidation, cyclohexylhydroperoxide, reaction mechanism

中图分类号:

O643

徐丽婷, 邢娜, 吴琼, 马喜彤, 邢永恒. 铁(Ⅲ)的氮杂环配合物的合成、结构及对环己烷氧化的催化性能[J]. 应用化学, DOI: 10.3724/SP.J.1095.2014.30439.

XU Liting, XING Na*, WU Qiong, MA Xitong, XING Yongheng*. Synthesis, Structure of an Iron(Ⅲ) Complex Containing N-Donor Ligand and Its Catalytic Activity for Cyclohexane Oxidation[J]. Chinese Journal of Applied Chemistry, DOI: 10.3724/SP.J.1095.2014.30439.

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