含二茂铁基大环多胺化合物的合成、结构及催化性能  

Synthesis, structure and catalytic properties of macrocyclic polyamine compounds containing ferrocenyl moiety

作　　者：杨晓升[1] 郝虎君[1] 卢忠林[1] 

机构地区：[1]北京师范大学化学学院,北京100875

出　　处：《中国科技论文》2012年第3期210-214,共5页China Sciencepaper

基　　金：高等学校博士学科点专项科研基金新教师基金资助项目(200800271020);教育部新世纪优秀人才支持计划(NCET-08-0054)

摘　　要：大环多胺化合物由于其在生物模拟和催化反应方面的性能备受关注。以N,N-二甲基二茂铁甲胺以原料,合成了一个含有二茂铁基的大环多胺化合物6,通过红外、核磁和质谱等手段对化合物6和重要中间体进行了表征,得到了其单晶结构。化合物6.HCl的晶体结构表明,每个不对称单元内包括1个N(2)原子上质子化的化合物6和1个游离的氯离子,分子内存在较强的N—H…N氢键作用。质子化的大环多胺单元之间通过N—H…Cl氢键连接形成了一维的链状超分子结构。动力学实验结果表明,与甲氧根催化反应的二级速率常数相比,二茂铁基[12]aneN3大环多胺6的Cu(II)配合物在甲醇介质中可以提高杀螟松甲醇解反应的效率达1.64×104倍。同时,该化合物对其他含有P==S键的农药也具有良好的催化降解效果。Macrocyclic polyamines have been received much attention due to their importance in bio-mimic and catalysis. A macrocyclic polyamine compound containing ferrocenyl group, 6, has been synthesized from N, N-dimethylaminomethylferrocene and characterized by IR, ^1H-NMR, ^13C-NMR and single-crystal X-ray diffraction. Compound 6.HC1 consists of significant intramolecular N--H...N hydrogen bonding interactions, and each asymmetry unit contains a N（2） protonated compound 6 and a chloride ion. The protonated macrocyclic polyamines are linked by N--H...C1 hydrogen bonding interactions, forming a one-dimensional supramolecular architecture. Cu（II） complex of ligand 6 can accelerate the methanolysis of fenitrothion by 1.64×10^4 folds in terms of second-order rate constant when compared to that of the methoxide-catalyzed reaction. Furthermore, the complex can greatly catalyze the methanolysis of other P=S containing pesticide.

关 键 词：大环多胺 二茂铁 晶体结构 甲醇解 有机磷农药 

分 类 号：O627.8[理学—有机化学]