CAJ | 학술논문

由对羟基苯甲酸及其邻、间位异构体与1,8-二氯代-3,6-二氧杂辛烷出发,经多步反应制备了聚醚桥连的二异羟肟酸对、间和邻位异构体.借助Chem3D(MM2)模拟了配体分子的最低能量构象图,解释了它们在IR谱、1H NMR谱和配位性能等之间的差异.在吡啶溶液中和不同温度下,测定了钴(Ⅱ)配合物的饱和吸氧量,求出了它们的氧加合常数KO2和热力学参数DH°, DS°,并将其应用于对二甲苯的催化氧化反应中,考察了聚醚桥链的键连部位对配合物的氧合与催化性能的影响.
유대간기분갑산급기린、간위이구체여1,8-이록대-3,6-이양잡신완출발,경다보반응제비료취미교련적이이간우산대、간화린위이구체.차조Chem3D(MM2)모의료배체분자적최저능량구상도,해석료타문재IR보、1H NMR보화배위성능등지간적차이.재필정용액중화불동온도하,측정료고(Ⅱ)배합물적포화흡양량,구출료타문적양가합상수KO2화열역학삼수DH°, DS°,병장기응용우대이갑분적최화양화반응중,고찰료취미교련적건련부위대배합물적양합여최화성능적영향.
Three new p-, m- and o-isomers of polyether-bridged dihydroxamic acids were prepared in multi-step reaction from 1,8-dichloro-3,6-dioxaoctane and p-, m- or o-hydroxy-benzoic acid. The differences of the ligands in IR, 1H NMR and their complexation performance on cobalt ion were well explained by the energy-minimized models in Chem3D (MM2). Saturated oxygen uptaken by the cobalt (II) complexes were measured in pyridine solvent at different temperatures, and the equilibrium constants Ko2 and thermodynamic parameters DH°, DS° for oxygenation were calculated. Meanwhile the complexes are applied in the catalytic oxidation of p-xylene successfully. The influences of the bonding position of the polyether-bridge on dioxygen-affinities and catalytic performance of the complexes are also discussed.