Study of kinetics and mechanism of the acid dissociation of copper(II) complex of novel C-functionalized macrocyclic dioxotetraamines

Lin HK.; Kondiano AB.; Su XC.; Kou FP.; Chen YT.; Zhu SR.

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Study of kinetics and mechanism of the acid dissociation of copper(II) complex of novel C-functionalized macrocyclic dioxotetraamines

机译：新型C-官能化大环二氧四胺的铜（II）配合物酸解离的动力学和机理研究

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The kinetics of the acid dissociation of copper(II) complexed of novel C-functionalized macrocyclic dioxotetraamines has been studied by means of a stopped-flow spectrophotometer. The acid dissociation rate follows the law V-d = C(com)kK(1)K(2)H(2)/(1 + K1H + K1K2H2). From the experimental facts we have obtained, the dissociation kinetics are interpreted by a mechanism involving the negatively charged carbonyl oxygen of the complex being rapidly protonated in a pre-equilibrium step, the rate-determining step being intramolecular hydrogen (enolic tautomer) migration (to imine nitrogen). The dissociation rare reached a plateau in the strongly acidic solution. By means of temperature coefficient method, Delta H-phi, Delta S-phi of the pre-equilibrium step and Delta H-not equivalent to, Delta S-not equivalent to of the rate-determining step were obtained. The results of 13-membered macrocyclic dioxotetraamines have been discussed. The influence of the substituents to the acid dissociation rates has also been discussed. The Bronsted type linear flee energy relationships do also exist in these C-functionalized dioxotetraamine copper(II) complexes. (C) 1998 Elsevier Science Ltd. All rights reserved [References: 31]

机译：新型的C-官能化的大环二氧四胺络合的铜（II）的酸离解动力学已通过停止流式分光光度计进行了研究。酸解离速率遵循定律V-d = C（com）kK（1）K（2）H（2）/（1 + K1H + K1K2H2）。从我们获得的实验事实中，解离动力学是通过一种机制来解释的，该机制包括在预平衡步骤中使复合物带负电荷的羰基氧迅速质子化，速率确定步骤是分子内氢（烯丙基互变异构体）迁移（亚胺氮）。在强酸性溶液中，这种解离罕见地达到了平稳状态。通过温度系数法，求出了预平衡步骤的ΔH-phi，预平衡步骤的ΔS-phi和速率决定步骤的ΔH-不等价，ΔS-不等价。讨论了13元大环二氧四胺的结果。还讨论了取代基对酸解离速率的影响。这些C功能化的二氧四胺铜（II）配合物中也确实存在布朗斯台德型线性逃逸能关系。（C）1998 Elsevier Science Ltd.保留所有权利[引用：31]

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来源
《Polyhedron: The International Journal for Inorganic and Organometallic Chemistry》 |1998年第26期|共7页
作者
Lin HK.; Kondiano AB.; Su XC.; Kou FP.; Chen YT.; Zhu SR.;
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正文语种 eng
中图分类化学;无机化学;
关键词
Macrocyclic dioxotetraamines; Acid dissociation; Kinetics; Mechanism; Copper(ii) complex; Aqueous-media; Isomerization kinetics; Nickel(ii) complexes; Polyamine complexes; Blue cation; Ligands;

机译：大环二氧四胺;酸离解;动力学;机理;铜（ii）络合物;水介质;异构化动力学;镍（ii）络合物;多胺络合物;蓝色阳离子;配体;

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1. Study of kinetics and mechanism of the acid dissociation of copper(II) complex of novel C-functionalized macrocyclic dioxotetraamines [J] . Lin HK., Kondiano AB., Su XC., Polyhedron: The International Journal for Inorganic and Organometallic Chemistry . 1998,第25a26期

机译：新型C-官能化大环二氧四胺的铜（II）配合物酸解离的动力学和机理研究
2. KINETICS AND MECHANISM OF THE ACID DISSOCIATION OF COPPER(II) COMPLEX OF NOVEL C-FUNCTIONALIZED MACROCYCLIC DIOXOTETRAAMINES [J] . Kou FP., Lin HK., Chen WD., Polyhedron: The International Journal for Inorganic and Organometallic Chemistry . 1997,第12期

机译：新型C-官能化大环二氧四环酰胺铜（II）配合物的酸离解动力学及机理
3. Kinetice and mechanism of acid dissociation of nickel(II) complexes of novel c-functionalized macrocyclic dioxotetraamines [J] . Huakuan Lin, Shourong Zhu Journal of Coordination Chemistry . 1999,第3期

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4. Fundamental Mechanisms Controlling Copper Electrodeposition.A Kinetic Study Of The Autocatalytic Reduction Of Cu(II) IonBy 3-Mercaptopropanesulfonic acid [C] . Robert A. Binstead, Robert Mikkola, Jeffrey M. Calvert AIChE annual meeting . 2003

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Study of kinetics and mechanism of the acid dissociation of copper(II) complex of novel C-functionalized macrocyclic dioxotetraamines

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