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  

Synthesis,Structure of an Iron(Ⅲ) Complex Containing N-Donor Ligand and Its Catalytic Activity for Cyclohexane Oxidation

作　　者：徐丽婷[1] 邢娜[1] 吴琼[1] 马喜彤 邢永恒[1] 

机构地区：[1]辽宁师范大学化学化工学院,大连116029

出　　处：《应用化学》2014年第6期707-714,共8页Chinese Journal of Applied Chemistry

基　　金：国家自然科学基金(21071071;21371086);国家青年科学基金(21306073);大连市优秀青年科技人才基金(2012J21DW007)~~

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。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-1 H-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; HNO3has 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.

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 

分 类 号：O643[理学—物理化学]