【摘要】 本文合成了桥基分别为OH^-,Cl^-,Br^-,I^-,SCN^-和N₃^-的2,6一二甲酰基吡啶缩丙二胺的大环双锕（Ⅱ）配合物,通过pH滴定法对其在水溶液中的羟合作用进行了研究,通过Pq分析、紫外光谱和离子选择性电报的测定,可知在pH=6.5～10.5范围内配合物的基本结构保持不变,并在其轴向键合羟基、在pH=8.0～10.1体系中主要以—羟合物为主,其羟合常数的大小随桥基而异,可分为三组。以I^-,SCN^-为桥基的配合物羟合常数最大,Cl^-,OH^-,Br^-则次之,而N₃^-最小,通过光照法对配合物与O₂^-的反应进行了研究,结果表明配合物与O₂^-反应的活性随桥基而异,且与一级羟合常数的顺序有一致关系。更多还原

【Abstract】 Some dicopper macrocyclic complexes with bridge OH^-, Cl^-,Br^-,I^-, SCN^-. N₃^-were synthesized by condensation reaction of 2, 6-diformylpyridine with 1,3-diaminopropane. The hydroxylation of these complexes in aqueous solution was studied by pH-titration. Data obtained from pq analysis, electronic spectrum and titration by ion selective electrode showed that the basic structures of complexes were kept to be constant in the range of pH 6.5 to 10.5 and hydroxyl ion bound to copper ion in axis direction of complexes. The monohydroxo- complexes were the major species in pH=8.0～10.1. The hydroxylation constants of complexes varied with their bridges and can be divided into three groups. Comlexes with I^-, SCN^-bridge have the largest hydroxylation constants, those with Cl^-, OH^- and Br^-bridge have less constants, and that with N₃^- bridge has the least constant. The reaction of complexes with O₂^- were studied by illumination method. Results showed that the activities of complexes reacting with O₂^- varied with bridges and agreed with the order of hydroxylation constants of these complcxcs.更多还原