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首页> 外文期刊>Journal of Solution Chemistry >Thermodynamics, Chemical Speciation and Complex Formation Equilibria Studies of Binary and Mixed Ligand Complexes of Cu(II) with 2,2'-Bipyridyl and Some Aromatic Diamines
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Thermodynamics, Chemical Speciation and Complex Formation Equilibria Studies of Binary and Mixed Ligand Complexes of Cu(II) with 2,2'-Bipyridyl and Some Aromatic Diamines

机译：Cu（II）与2,2'-联吡啶和某些芳香族二胺的二元和混合配体配合物的热力学，化学形态和配合物形成平衡研究

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摘要

The formation of mixed ligand complexes of Cu(II) with 2,2'-bipyridyl (Bipy) in the presence of some selected aromatic diamines (L) (L = 3,4-diamino benzoic acid (DABA), 2-hydazinopyridine (hzpy) or 4-chloro-o-phenylenediamine has been studied by pH-metric titrations. Potentiometric measurements show that ternary complexes are formed in a simultaneous manner. The pH-titrations of the reaction mixtures are shown to yield 1:1:1 ternary complex formation. The equilibrium and formation constants of the resulting ternary complexes have been calculated at I = 0.1 mol center dot dm(-3) of NaNO3. The order of stability in terms of the secondary ligands has been found to be DABA > hzpy > CAPA. The stability of ternary complexes was quantitatively compared with their corresponding binary complexes in terms of the parameters Delta log(10) K, Delta log(10) beta and log(10) X. The concentration distributions of various species formed in solution were also evaluated as a function of pH. In addition, the effect of temperature on both the ionization process of the ligands and complex formations for Cu-Bipy-L ternary systems was studied. The thermodynamic parameters were calculated from the temperature dependence of the equilibrium constants and are discussed. The structure of the Cu(II) complexes have been geometrically optimized using the parameterized PM3 semiempirical method.
机译：在某些选定的芳族二胺（L）（L = 3,4-二氨基苯甲酸（DABA），2-肼基吡啶（）的存在下，Cu（II）与2,2'-联吡啶（Bipy）的混合配体络合物的形成hzpy）或4-氯-邻苯二胺已通过pH滴定法进行了研究。电位测量表明三元络合物是同时形成的，反应混合物的pH滴定表明可生成1：1：1三元在NaNO3的I = 0.1 mol中心点dm（-3）处计算出三元配合物的平衡和形成常数，发现二级配体的稳定性顺序为DABA> hzpy> CAPA。根据参数Delta log（10）K，Delta log（10）beta和log（10）X对三元配合物的稳定性及其相应的二元配合物进行了定量比较。还根据pH进行评估。此外，研究了温度对Cu-Bipy-L三元体系的配体电离过程和配合物形成的影响。根据平衡常数的温度依赖性计算热力学参数并进行讨论。使用参数化的PM3半经验方法对Cu（II）配合物的结构进行了几何优化。

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