铜（Ⅱ）－4－（吡啶－2′－甲基）－1，4，7，10－四氮杂环十三烷－11，13－二酮－α－氨基酸（5－取代邻菲罗啉）三元配合物的稳定性研究  

STUDIES ON THE STABILITY OF Cu(Ⅱ) 4 (PYRIDYL 2′ METHYLENE) 1,4,7,10 TETRAAZACYCLOTRIDECANE 11,13 DIONE α AMINOACID (5 SUBSTITUTED PHENANTHROLINE) TERNARY COMPLEXES

作　　者：于丽[1] 林华宽[1] 卜显和[1] 安道利[1] 陈荣悌[1] 

机构地区：[1]南开大学化学系

出　　处：《化学研究与应用》1996年第3期381-386,共6页Chemical Research and Application

摘　　要：用ｐＨ法在２５．０±０．１℃，Ｉ＝０．１ｍｏｌ·ｄｍ－３ＫＮＯ３条件下，测定铜（Ⅱ）－４－（吡啶－２′－甲基）－１，４，７，１０－四氮杂环十三烷－１１，１３－二酮－α－氨基酸（５－取代邻菲罗啉）三元配合物的稳定常数；比较了带吡啶甲基二氧四胺大环配体和二氧四胺大环配体与Ｃｕ（Ⅱ）的配位能力、配位方式；研究了该三元体系配合物稳定性与配体α－氨基酸酸碱强度之间的直线自由能关系；探讨了Ｃｕ（Ⅱ）和５－取代邻菲罗啉之间的ｄ－ｐ反馈π键以及邻菲罗啉取代基Ｈａｍｍｅｔｔ诱导效应与该三元配合物稳定性之间的关系。讨论了４－（吡啶－２′－甲基）－１，４，７，１０－四氮杂环十三烷－１１，１３－二酮和４－（喹啉－２′－甲基）－１，４，７，１０－四氮杂环十三烷－１１，１３－二酮与Ｃｕｘｐｈｅｎ所形成配合物的不同空间结构及其对配合物稳定性产生的影响。The stability constants of Cu(Ⅱ) 4 (pyridyl 2′ methylene) 1,4,7,10 tetraazacyclotridecane 11,13 dione α aminoacid (5 substituted phenanthroline) ternary complexes were measured by pH titration method at 25.0±0.1C,I=0.1mol·dm 3 KNO 3.The coordinating ability bwtween Cu(Ⅱ) andmacrocyclic dioxotetraamine ligands with pyridyl 2′ methylene as a functional pendant and between Cu(Ⅱ) and macrocyclic dioxotetraamine ligands without pendant were compared.The linear free energy relationships between the stability constants of the ternary complexes and the protonation constants of ligands α aminoacid (5 subtituted phenanthroline) were demonstrated.The d p back bonding formed between Cu(Ⅱ) and 5 subtituted phenanthroline and the relationship between the induce effect of Hammett parameters of substituents and stability of ternary complexes were discussed.The different space structures of the complexes formed by 4 (pyridyl 2′ methylene) 1,4,7,10 tetraazacyclotridecane 11,13 dione and 4 (quinoline 2′ methylene) 1, 4,7,10 tetraazacyclotridecane 11,13 dione and 4 (quinoline 2′ methylene) 1, 4,7,10 tetraazacyclotridecane 11,13 dione respectively with Cuxphen and the their effect on the complex staility were discussed.

关 键 词：稳定性 Α-氨基酸 甲基吡啶 大环配体 铜配合物 

分 类 号：O614.121[理学—无机化学]