Abstract

Complex formation properties of a novel water soluble thiazolyloxime 2-(4-methylthiazol-2-yl)-2-(hydroxyimino)acetic acid (H₃L¹) with Cu²⁺ and Ni²⁺ were investigated in solution by potentiometrical and spectral (UV–Vis, EPR, NMR) methods. All Cu²⁺ and most of Ni²⁺ complex species detected in solution were found to have square-planar MN₄ core with oxime and heterocyclic nitrogen atoms which was rationalized in terms of destabilizing effect of repulsive interaction between oxygen atom of carboxylic group and nitrogen atom of thiazole ring in N,O-coordinated ligand conformation. It has been found that stability of metal complexes in a series of oxime ligands is dependent upon basicity of nitrogen atom of oxime group. The thiazolyloxime forms less stable complexes with Cu²⁺ but stronger ones with Ni²⁺ ions when compared to parent 2-(hydroxyimino)propanoic acid. The lower stability obtained for Cu²⁺ complexes was elucidated in terms of negative inductive effect of the thiazole and nitrile substituents as well as an effect of intramolecular attractive interaction between thiazolyl sulfur and oxime oxygen atoms in thiazolyloxime. In the case of Ni²⁺ the complexes formed are square-planar and it is why thiazolyl ligand is more effective in metal ion binding than simple 2-(hydroxyimino)propanoic acid forming only octahedral species. The solid state structure of the Co³⁺ complex K₃[Co(HL¹)₃]·5.5H₂O (1) was studied by X-ray analysis. The thiazolyloxime ligand is coordinated to Co³⁺ via oxime nitrogen and carboxylate oxygen atoms forming five-membered chelate rings.

Graphical Abstract

Coordination properties of 2-(4-methylthiazol-2-yl)-2-(hydroxyimino)acetic acid with Cu²⁺, Ni²⁺ and Co³⁺ were investigated by potentiometry, UV–Vis, EPR, and NMR spectroscopy and X-ray crystallography.

Author Keywords: Crystal structure; Metal binding; Oxime; Thiazole; 3d-Metals

Article Outline

1. Introduction

2. Experimental

2.1. Preparations

2.1.1. 2-(4-Methylthiazol-2-yl)-2-(hydroxyimino)acetic acid (H₃L¹)

2.1.2. K₃[Co(HL¹)₃]·5.5H₂O (1)

2.2. Potentiometric and spectroscopic studies

2.3. Crystallography

3. Results and discussion

3.1. Molecular structure of H₃L¹

3.2. Potentiometric study

3.3. Molecular structure of K₃[Co(HL¹)₃]·5.5H₂O

4. Conclusions

Acknowledgements

References

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