Metal Complexes with Macrocyclic Ligands. Part XXI. A nonlinear relationship between the stability of Cu2+ complexes and their complexation rate with 1,4,8,11-tetraazacyclotetradecane
作者:Yi-he Wu、Thomas A. Kaden
DOI:10.1002/hlca.19850680613
日期:1985.9.25
by a nonlinear curve-fitting procedure. For nearly all systems studied, the rate constant k, describing the reaction between the 1:1 complex CuL and the monoprotonated form of the macrocycle CyH, was obtained. The nonlinear relationship between log k and log KCuL and its nature is discussed. It is shown that the inverse relationship between reactivity and stability described by others is only a special
1,4,8,11-四氮杂十四烷(Cy)与一系列Cu(II)配合物之间的反应动力学(1)CuL(L)=乙醇酸,丙二酸,琥珀酸,吡啶甲酸,甘氨酸,亚氨基二乙酸酯,次氮基三乙酸酯,N -(2-羟乙基)乙二胺三乙酸酯,乙二胺,1,3-二氨基丙烷,二亚乙基三胺和N,N-双(3-氨基丙胺)在25°和I = 0.5(KNO 3)上进行分光光度法研究。通过分析在不同pH值下获得的log k obs / log [L]曲线,可解析双分子速率常数k (表3)通过非线性曲线拟合程序获得。对于几乎所有研究的系统,均获得了速率常数k,该常数描述了1:1复杂CuL与大环CyH单质子化形式之间的反应。讨论了log k和log K CuL之间的非线性关系及其性质。结果表明,其他人描述的反应性和稳定性之间的反比关系只是更一般的方程式的一种特殊情况。这里描述3。