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采用pH法,在25.0±0.1℃,I=0.1mol·dm_3(KNO_3条件下,测定了13-取代苄基-1,4,8,11-四氮杂环十四烷-12,14-二酮的质子化常数及其与CU(Ⅱ)配位的平衡常数讨论了配体与金属离子的配位方式.在25.0±0.1℃,离子强度为0.1mol·dm~3(KNO_3)下,采用分光光度法,研究了这此配体铜(Ⅱ)配合物的酸分解动力学行为.探讨了配合物酸分解反应机理,得到了速控步的速率常数.发现配位反应平衡常数与配体的质子化常数及配合物酸分解反应速率常数之间存在较好的Hammett型和Br(?)nsted型直线自由能关系.同时探讨了取代基对配合物生成及酸分解的影响情况.
Under the condition of 25.0 ± 0.1 ℃, I = 0.1mol · dm_3 (KNO_3), the content of 13-substituted benzyl-1,4,8,11-tetraazacyclotetradecane-12,14- The protonation constants of ketones and their coordination constants with CU (Ⅱ) were discussed. The coordination modes of the ligands and metal ions were discussed. Under the condition of 25.0 ± 0.1 ℃ and the ionic strength of 0.1mol · dm ~ 3 (KNO 3) Spectrophotometry was used to study the kinetic behavior of the copper (Ⅱ) complex. The mechanism of the acid decomposition reaction was discussed and the rate constant of the rate-controlling step was obtained. It was found that the equilibrium constant of ligand reaction and ligand And the linear relationship between Hammett type and Br (?) Nsted type linear free energy exists between the protonation constants and the rate constants of the complexation of the complex. The effects of the substituents on the complex formation and acid decomposition are also discussed.