配合物稳定性和配体酸碱强度之间的直线自由能关系──铜（Ⅱ）、锌（Ⅱ）－芬布芬－α－氨基酸三元配合物体系  

LINEAR FREE ENERGY RELATIONSHIP BETWEEN STABILITY OF COMPLEX COMPOUND AND BASICITY OF LIGAND──Cu(Ⅱ)-AND Zn(Ⅱ) -FENBUFEN-α-AMINO ACID TERNARY COMPLEXES SYSTEM

作　　者：田君濂[1] 李延团[1] 毕思玮[1] 刘树祥[1] 

机构地区：[1]曲阜师范大学化学系

出　　处：《无机化学学报》1994年第1期30-34,共5页Chinese Journal of Inorganic Chemistry

摘　　要：在２５±０．１℃，Ｉ＝０．１ｍｏｌ·ｄｍ－３ＫＮＯ３条件下，８０％（ｖ／ｖ）ＤＭＳＯ—Ｈ２Ｏ混合溶剂中，应用ｐＨ法测定了甘氨酸，Ｌ一缬氨酸，Ｌ－异亮氨酸，Ｌ－脯氨酸，Ｌ－丝氨酸，ＤＬ－苯丙氨酸等六种α－氨基酸（缩写为α－ＡＡ，记为Ｂ配体）的酸离解常数，铜（Ⅱ）－α－氨基酸．锌（Ⅱ）－α－氨基酸二元配合物的稳定常数及铜（Ⅱ）－芬布芬－α－氨基酸（芬布芬缩写为Ｆｅｎ，记为Ａ配体）和锌（Ⅱ）－芬布芬－α－氨基酸三元配合物的稳定常数．实验发现，在下面三对参数之间，即ｌｏｇβ１０２与ｐＫ，ｌＯｇβ１１１；与ｐＫ及１０ｇβ１１１与ｌｏｇβ１０２，均存在良好的直线自由能关系．用△ｌｏｇＫＭ和△ｌｏｇβ１１１两个参量描述了三元配合物相对于母体二元配合物的稳定性．讨论了溶剂的性质，配合物分子内配体之间的疏水作用，芳环之间的堆积作用对配合物稳定性的影响．The dissociation constants of α-amino acid and formation constants of M(Ⅱ)-α-aminoacid(B) binary complexes and M(Ⅱ)-Fenbufen(A)-α-amino acid ternary complexes [M(Ⅱ)=Cu(Ⅱ), Zn(Ⅱ)] were determined by pH method at 25±0.1℃ in the presence of 0.1mol / dm3 KNO3 in 80% (V/V) DMSO-H2O mixed solvent. The α-amino acid used wereglycine, L-valine, L-isoleucine, L-proline. L-serine, and DL-phenylalanine. It has been foundthat linear free energy relationship (LFER) exist nicely between the following parameter pairslogβ102 and pK, logβ111 and pK and logβ1111 and logβ102. The logKM(= logβ111-logβ110-logβ101)and △logβ111(△logβ111-1 / 2logβ120-1 / 21ogβ102-log2) are used to characterize the stability ofternary complexes related to the stability of parent binary complexes. The influence ofintramolecular ligand-ligand interaction on the stability of binary and ternary complexes wasdiscussed.

关 键 词：稳定性 酸碱度 自由能 络合物 配体 

分 类 号：O641.4[理学—物理化学]