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 |
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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pK2B,lOgβ111;与pK2B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。 |
关键词: 稳定常数 自由能关系 芬布芬 α-氨基酸 |
基金项目: |
Abstract: 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 pK2B, logβ111 and pK2B and logβ111 and logβ102. The logKM(= logβ111-logβ110-logβ101)and △logβ111(△logβ111-1/2logβ120-1/2logβ102-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. |
Keywords: stability constant free energy relationship Fenbufen α-amino acid |
投稿时间:1992-11-04 |
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田君濂,李延团,毕思玮,刘树祥.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[J].无机化学学报,1994,10(1):30-34. |
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