取代苯基重氮盐-冠醚络合物的成键作用  

The Bonding Action in Complexes of Substituted Phenyldiazonium salts With Crown Ether

作　　者：孙祥玉[1] 赵瑶兴[1] 

机构地区：[1]中国科学技术大学研究生院

出　　处：《中国科学技术大学学报》1993年第2期169-174,共6页JUSTC

基　　金：国家自然科学基金;北京分子动态和稳态结构国家实验室资助

摘　　要：报道一系列取代苯基重氮盐及其18-冠醚-6络合物的远红外光谱、^(13)C核磁共振和FAB-质谱,由主体和客体形成络合物前后的光谱变化和这类络合物质谱中表征[M-BF_4]^+离子峰的相对丰度,结合取代基效应讨论络合物的成键状况,推测这类络合键除冠醚氧与重氮盐α-氮正电中心相互作用外,尚存在α-电子由重氮盐β-氮向冠醚氧转移的反馈作用。用Hückel分子轨道法对重氮盐各原子电荷密度分布计算的结果支持上述推论。The Far-infrared ^(13)C NMR and FAB—MS of a series of substituted phenyldiazonium salts and their 18-crown-6 complexes are examined to discuss the bonding condition from the spectrum changes before and after complex formation, the relative abundance of [M-BF_4]^+ ion peak of these complexes in FAB-MS, and the substituent effects. It is inferred that there exists a back donation of π-electrons from the β-nitrogen atoms of diazonium salts to the oxegen atoms of crown ether besides the interaction between the oxegen atoms of crown ether and the positive charge in α-nitrogen of diazonium salts. The distribution of electron density in diazonium salts is calculated by using Hücked molecular orbital method. The results support the above inference.

关 键 词：芳基重氮盐 冠醚 络合物 成键作用 

分 类 号：O641.4[理学—物理化学]