尾式卟啉铁(Ⅲ)电化学性质研究──Ⅱ.二甲胺基/二乙胺基尾式卟啉铁轴向效应的循环伏安行为
STUDIES OF ELECTROCHEMICAL CHARACTERISTICS──OF NEW TAILED IRON(Ⅲ) PORPHYRIN Ⅱ. AXIAL COORDINATION EFFECTS IN CYCLIC VOLTAMMETRY BEHAVIOR OF TAILED PORPHYRIN IRON(Ⅲ) COMPLEXES
作者单位
王清民 吉林大学化学系, 长春, 130023 
师同顺 吉林大学化学系, 长春, 130023 
赵东源 吉林大学化学系, 长春, 130023 
陶建忠 河南技术师范学院 
张树国 吉林大学化学系, 长春, 130023 
曹锡章 吉林大学化学系, 长春, 130023 
摘要: 本文用循环伏安法研究了一类新型生物模型化合物-氯化-间-[邻-(4-二甲胺基/二乙胺基丁酰胺基苯基)三苯基]卟啉铁(Ⅲ)在不同抗衡阴离子、NO及轴向含N有机碱存在下的电化学行为。结果表明:(1)抗衡阴离子对电对Fe(Ⅲ)/Fe(Ⅱ)半波电位的影响顺序为Cl->Br->OAc->ClO4-.对电对Fe(Ⅱ)/Fe(Ⅰ)的影响则相反。(2)NO的配位改变了尾端叔胺的配位状态,由于NO与铁卟啉配位而被活化。(3)由于含N有机碱的轴向配位,使Fe(Ⅲ)/Fe(Ⅱ)和Fe(Ⅱ)/Fe(Ⅰ)电对的半波电位发生了很大的位移,位移的变化不仅通过轴向配位,而且通过配位还原来实现。本文还简要地讨论了尾端叔胺的电位调谐作用。
关键词: 尾式卟啉铁(Ⅲ)  轴向效应  循环伏安
基金项目: 
Abstract: The electrochemical behavior of two new biological compounds-tailed porphyrin iron(Ⅲ),meso-mono(o-(4-dimethyl/diethyl amino) butyramidophebyl) triphenyl porphyrin iron(Ⅲ)(abb.:PmFe(Ⅲ)X and PeFe(Ⅲ)Cl, respectively) was investigated by cyclic voltammetry in thepresence of different counter ions. The results demonstrated that (1) the sequences of counteroin effect on half-wave electric potentials of Fo(Ⅲ) / Fe(Ⅱ) and Fe(Ⅲ)/Fo(Ⅰ) electric pairswere as follows, respectively:Cl-> Br-> OAc-> ClO4- and CIO4- > OAc- > Br- >Cl-, (2) theaxial coordination of NO molecule could change the coordination state of terminal tertiaryammes of tailed porphyrin iron. Furthermore, NO molecule was actuated considerably and (3)the axial coordination of organic bases containing nitrogen atom could make the half--waveelectric potentials of Fo(Ⅲ) / Fe(Ⅱ) and Fe(Ⅱ) / Fe(Ⅰ) electric pairs shift significantly, whichwas not only relevent to axial coordination of organic bases but also actual coordination reduction reaction under certain circumstances.
Keywords: tailed porphyrin iron(Ⅲ)  axial effect  cyclic voltammetry
投稿时间:1992-10-15 
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王清民,师同顺,赵东源,陶建忠,张树国,曹锡章.尾式卟啉铁(Ⅲ)电化学性质研究──Ⅱ.二甲胺基/二乙胺基尾式卟啉铁轴向效应的循环伏安行为[J].无机化学学报,1994,10(1):19-24.
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