Investigations of ternary complexes of Co(II) and Ni(II) with oxydiacetate anion and 1,10-phenanthroline or 2,2′-bipyridine in solutions

D. Wyrzykowski, J. Pranczk, D. Jacewicz, A. Tesmar, B. Pilarski, L. Chmurzyński
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引用次数: 14

Abstract

AbstractPotentiometric (PT) and conductometric (CT) titration methods have been used to determine the stoichiometry and formation constants in water for a series of ternary complexes of Co(II) and Ni(II) involving the oxydiacetate anion (ODA) and 1,10-phenanthroline (phen) or 2,2′-bipyridine (bipy) ligands, namely [Co(ODA)(phen)(H2O)], [Co(ODA)(bpy)(H2O)], [Ni(ODA)(phen)(H2O)] and [Ni(ODA)(bpy)(H2O)]. The ternary complex formation process was found to take place in a stepwise manner in which the oxydiacetate ligand acts as a primary ligand and the phen or bipy ligands act as auxiliary ones. The stability of the ternary complexes formed is discussed in the relation to the corresponding binary ones. Furthermore, the kinetics of the substitution reactions of the aqua ligands in the coordination sphere of the Ni-ODA and Co-ODA complexes to phen or bipy were studied by the stopped-flow method. The kinetic measurements were performed in the 288–303 K temperature range, at a constant concentration of phen or bipy and at seven different concentrations of the binary complexes (4–7 mM). The influence of experimental conditions and the kind of the auxiliary ligands (phen/bipy) on the substitution rate was discussed.
Co(II)和Ni(II)与氧化二乙酸阴离子和1,10-菲罗啉或2,2 ' -联吡啶三元配合物的研究
摘要用电位滴定法(PT)和电导滴定法(CT)测定了一系列Co(II)和Ni(II)三元配合物在水中的化学计量学和形成常数,这些配合物包括双乙酸氧阴离子(ODA)和1,10-菲罗啉(phen)或2,2 ' -联吡啶(bipy)配体,即[Co(ODA)(phen)(H2O)], [Co(ODA)(bpy)(H2O)], [Ni(ODA)(phen)(H2O)]和[Ni(ODA)(bpy)(H2O)]。发现三元配合物的形成过程是一个循序渐进的过程,其中氧化二乙酸酯配体作为初级配体,苯乙烯或双苯乙烯配体作为辅助配体。讨论了形成的三元配合物的稳定性与相应的二元配合物的关系。此外,采用停流法研究了Ni-ODA和Co-ODA配合物配位球中水基配体对苯乙烯或苯乙烯的取代反应动力学。动力学测量在288 ~ 303 K温度范围内进行,在固定浓度的苯乙烯或苯乙烯和七种不同浓度的二元配合物(4 ~ 7 mM)下进行。讨论了实验条件和辅助配体(phen/bipy)的种类对取代率的影响。
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