6-(5'-(8'-羟基喹啉)亚甲基)-1,4,8,11-四氮杂十一烷-5,7-二酮·5-取代邻菲罗啉合铜(Ⅱ)-铜(Ⅱ)或钴(Ⅱ)双核混配体系的稳定性研究

Stability Studies of Dinuclear Mixed-Coordinated Systems of 6-(5'-(8'-Hydroxyquinolinic)Methylene-1,4,8,11-Tetraazaundecane-5,7-Dione,5-Substituted 1,10-Phenanthroline-Copper (Ⅱ) with Cu^(2+) or Co^(2+) Complexes

本文合成了８－羟基喹啉取代的二氧四肢开链配体Ｌ并进行了红外、元素分析、核磁和质谱表征。在（２５ ±０．ｌ）℃，Ｉ＝０．１ｍｏｌ·ｄｍ－３ＮａＮＯ３条件下，运用ｐＨ电位滴定技术测定了双核混配体系Ｃ ｕ（Ⅱ）（或Ｃｏ（Ⅱ）-Ｌ-５-取代邻菲罗啉合铜（Ⅱ）配合物的稳定常数，并从滴定数据、物种分布曲线和文献结果对配合物可能的配位方式进行了讨论。我们发现在Ｃｕ （Ⅱ）-Ｌ－５．取代邻菲罗啉体系的质子化过程中，开链二氧四胺与Ｃｕ（Ⅱ）存在微弱配位，而邻菲罗琳和８－羟基喹啉与过渡金属离子的结合力远大于开链二氧四胺，因此在金属离子与配体比合适的情况下能稳定存在双核或异双核配位化合物。在质子化过程中，直线自由能关系尚成立而在多核混配体系中，直线自由能关系不存在，这说明在如此复杂的体系中很可能存在有趣的配体－配合物－金属离子的协同作用。

C-functionalized dioxotetraamine ligand L, 6- (5 '- (8'-hydroxyquinolinic) -methylene) - 1, 4, 8, 11-tetraazaundecane- 5, 7-dione, containing two independent chelating groups, was synthesized and characterized by elemental analysis, 1H MNR, IR and MS spectra. At 25. 0 1 0. 1℃, I = 0. lmol． din-3 NaNO3, pH titration has been performed to study the stability properties of L-5-substituted-1, 10-phenthamroline-Cu (Ⅱ) with proton, copper (Ⅱ) and cobalt (Ⅱ）, respectively. The ternary complexes have been show to possess interesting property due to the coordination interaction of the three chelating groups, 5-substituted-1, 10-phenanthroline, 8-hydroxyquinoline and dioxotetraamine. In addition, the possible coordination structures for the titration species have been suggested on the basis of titration results and literature report.