配合物生成反应速率常数与配体酸离解常数之间的直线自由能关系——Ⅴ.铜(Ⅱ)—2,9-二甲基邻菲啰啉与α-氨基酸和 N-苯基乙二胺生成三元配合物的动力学研究

Linear Free Energy Relationships Between Reaction Rate Constants of Complex Compounds and Acid Dissociation Constants of Ligands——Ⅴ.Kinetics of the Formation of Copper(Ⅱ)—2,9-Dimethylphenanthroline with α-Aminoacids and N-Phenylethylenediami

应用温度跃迁装置和断流分光光度计分别研究了铜(Ⅱ)—2,9-二甲基邻菲啰啉与α-氨基酸和N-苯基乙二胺在25℃、0.1mol·dm^(-3)KNO_3水溶液中的生成反应动力学.实验结果表明在铜(Ⅱ)—2,9-二甲基邻菲啰啉—α-氨基酸三元配合物的生成速率常数与配体α-氨基酸的酸离解常数之间存在着如下的直线自由能关系:logk_f=2.84+0.53pK_2.根据 Eigen 机理讨论了铜(Ⅱ)—2,9-二甲基邻菲啰啉—N-苯基乙二胺三元配合物的生成反应动力学.

The kinetics of eomplexation reaction of copper(Ⅱ)—2,9-dimethylphenanthroline[(CH_3)_2 phen] with α-aminoacids (Aa) and N-phenylethylenediamine (N-Ph-En) toform ternary systems has been studied by means of T-jump and stopped flow method at25℃ and I=0.1 mol·dm^(-3) (KNO_3) in aqueous solution.The results indicate theexistence of Br(?)nsted type linear free energy relationships between reaction rateconstants of Cu(Ⅱ)-(CH_3)_2 Phen-Aa ternary complex compounds and acid dissociationconstants of the second ligands,α-aminoacids,as followslogk_1=2.84+0.53pK_2,r=0.98The reaction rate constant of Cu(Ⅱ)—(CH_3)_2Phen—N-Pn-En ternary complexcompound has been evaluated and its kinetics being disscused by means of Eigenmechanism.