Zn2+、Cd2+和Hg2+与亚氨基噻唑烷酮配合物的稳定性常数和热力学参数的分光光度法研究

Z. B. Gemechu, T. Kebede, Ephrem G. Demissie, Girma W. Woyessa, S. Kassa
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引用次数: 3

摘要

以邻羟基苯基氯乙酰胺和硫氰酸钾为原料,合成了3-(2-羟基苯基)-2-亚氨基噻唑烷-4- 1杂环配体。首先用分光光度摩尔比法测定了标题配合物的化学计量学,得到Zn(II)和Cd(II)离子的M:L比为1:4,Hg(II)离子的M:L比为1:2。利用这些预定的M:L比,用相应的金属盐前驱体与标题配体在乙醇介质中制备了[Zn-L4]、[Cd-L4]和[Hg-L2]的配合物。通过元素分析、FTIR、1H和13CNMR、UV-Vis和电导等手段对合成的化合物进行了表征。用分光光度摩尔比法测定了这些配合物的稳定性常数。FTIR、1H NMR和13C NMR数据表明,所研究的配体为单齿配体,通过酚氧作为供体与Zn(II)和Cd(II)相互作用,通过酚氧和氮原子与Hg(II)相互作用。合成的配合物在298 K的DMSO中电导率值在122 ~ 133µSmol-1cm2之间,证实了配合物的电解性质。稳定性常数随温度升高而降低,证实了这些金属配合物在较高温度下不稳定。配合物ΔG的负值足够大,证实标题配合物是自发形成的。此外,还注意到反应的自发性随温度的升高而增加。这些配合物的稳定常数依次为Zn(II)>Cd(II)>Hg(II)。因此,总体结果与金属配合物的Irving-William系列稳定常数非常吻合。关键词:稳定常数,3-(2-羟基苯基)-2-亚氨基噻唑烷-4- 1,Irving-William系列,热力学参数,摩尔比法
本文章由计算机程序翻译,如有差异,请以英文原文为准。
Spectrophotometric study on the stability constants and thermodynamic parameters of Zn2+, Cd2+ and Hg2+ complexes with Imino Thiazolidinone
The heterocyclic ligand (L), 3-(2-hydroxy phenyl)-2-iminothiazolidin-4-one, was synthesized by the cyclocondensation of o-hydoxy phenyl chloroacetamide with potassium thiocyanate. The stoichiometries of the title complexes were first determined by spectrophotometric mole ratio method which gave rise to the M:L ratio of 1:4 in case of Zn(II) and Cd(II) and 1:2 in case of Hg(II) ions respectively. Using these predetermined M:L ratios, complexes of the formulas [Zn-L4], [Cd-L4] and [Hg-L2] were prepared accordingly using precursor of the corresponding metal salts with the title ligand in ethanol medium.  The synthesized compounds were characterized by elemental analysis, FTIR, 1H and 13CNMR, UV-Vis and conductometric measurement. Stability constants (Ks) of these complexes were investigated by spectrophotometric mole ratio method. The FTIR, 1H NMR and 13C NMR data revealed that the studied ligand function as monodentate ligand interacting through phenolic oxygen as donor with Zn(II) and Cd(II) and as bidentate ligand interacting through phenolic oxygen and nitrogen  atom with Hg(II). The synthesized complexes show conductivity values in the range of 122-133 µSmol-1cm2 in DMSO at 298 K which confirms the electrolytic nature of the complexes. The stability constants decreased with increased temperature, confirming that these metal complexes are not stable at higher temperature. Sufficiently large negative values of ΔG of complex confirm the spontaneous formation of the title complexes. Furthermore, it was noted that the spontaneity of the reaction increased with temperature. The stability constant of these complexes follow the sequence Zn(II)>Cd(II)>Hg(II). Therefore, the overall result is complying very well with the Irving-William series of stability constants of metal complexes.   Key words: Stability constants, 3-(2-hydroxyphenyl)-2-iminothiazolidin-4-one, Irving-William series, thermodynamic parameters, mole ratio method.
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