Physico-chemical Characterization of Some Metal Complexes Formed by Substituted Thiourea

G. Swarnabala, S. Khatavkar, G. Sadana, A. Bharadwaj
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Abstract

In view of unique physico-chemical observations affecting the geometry and various properties of the substituted thiourea complexes in literature along with several biological activities, N-(hydroxy)-N,N-diphenyl thiourea was taken up for study.  Complexes with geometries of high spin octahedral for iron(II), cobalt(II); tetrahedral & square planar for nickel(II); and dimeric square planar for copper chloride, copper perchlorate, copper acetate and distorted octahedral for copper nitrate were synthesized and characterized based on magnetic moments, visible spectra, diffuse reflectance spectra, electron spin resonance, infrared spectral studies, and thermal analysis. Interestingly, the nature of anion influenced the geometry, the complex from copper nitrate salt resulted in a distorted octahedral structure and complexes formed from copper chloride, copper perchlorate, copper acetate exhibited sub-normal magnetic moments, highly insoluble in the most common organic solvents and water. Based on these and spectral data, polymeric or square-planar dimeric geometry with sulfur bridging between copper atoms is proposed.  It was confirmed by the application of Bleaney-Bower’s equation for magnetic susceptibility, applicable to dimeric copper complexes. The overall thermal behavior of the ligand and complexes were observed and the detailed calculations interestingly lead to confirmation of the above proposed geometrical structures.
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取代硫脲形成的一些金属配合物的物理化学性质
鉴于文献中对取代硫脲配合物的几何形状和各种性质有独特的物理化学观察,并具有多种生物活性,本文选择了N-(羟基)-N,N-二苯基硫脲进行研究。铁(II)、钴(II)的高自旋八面体配合物镍(II)为四面体和方形平面;通过磁矩、可见光谱、漫反射光谱、电子自旋共振、红外光谱研究和热分析,合成了氯化铜、高氯酸铜、乙酸铜的二聚体方形平面和硝酸铜的畸变八面体。有趣的是,阴离子的性质影响了其几何形状,硝酸铜形成的配合物导致了扭曲的八面体结构,而氯化铜、高氯酸铜、醋酸铜形成的配合物表现出亚正常磁矩,在最常见的有机溶剂和水中高度不溶。基于这些数据和光谱数据,提出了铜原子之间有硫桥接的聚合物或方形平面二聚体几何结构。用适用于二聚铜配合物的Bleaney-Bower磁化率方程证实了这一结论。观察了配体和配合物的整体热行为,有趣的是,详细的计算证实了上述提出的几何结构。
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