环己烷氧化制取己二酸反应中铁卟啉催化剂结构与己二酸选择性关系的研究  

QSAR of Halogenated Iron-tetraphenylporphyrins for Oxidation of Cyclohexane to Adipic Acid

作　　者：徐晶[1] 佘远斌[1] 陈一霞[1] 郭雯[1] 

机构地区：[1]北京工业大学绿色化学与精细化工研究所,北京100022

出　　处：《化学工程与装备》2007年第1期9-11,共3页Chemical Engineering & Equipment

基　　金：国家自然科学基金面上项目(20576005)

摘　　要：以一系列不同取代基的氯化铁卟啉催化氧气氧化环己烷制取己二酸为模型反应,采用半经验PM3方法对这些铁卟啉化合物进行量子化学计算。将计算的微观结构参数(Fe- Cl键长、最高占据轨道能量EHOMO等)与宏观的催化剂性能实验数据(己二酸选择性)相结合,系统地研究了上述催化剂的结构与己二酸选择性的关系。并根据此定量关系,预测了T(p-CH_3)PPFeCl卟啉催化剂的选择性,经实验验证其预测的选择性与实验值相符。由此可见采用相关性模型来预测未知催化剂的选择性是可行的。A series of iron-tetraphenylporphyrins were used to catalyze the oxidation of cyclohexane to adipic acid by dioxygen.Their molecular frontier orbital energies EHOMO,Fe-Cl bond length etc,were investigated by means of the PM3 semi-empirical molecular orbital method.The quantitative structure activity relationships(QSAR)were investigated by combining adipic acid selectivity with EHOMO and Fe-Cl bond length of 5 catalysts.The catalytic selectivity of iron-tetraphenylporphyrin with substituted methyl group was predicted according to the quantitative structure -activity relationship,and the experimental results were consistent with the predicted ones,the results exhibited that it was possible for using model of structure-activity relationship to predict unknown catalysts.

关 键 词：环己烷 己二酸 选择性 铁卟啉 构效关系 

分 类 号：O643.32[理学—物理化学]