Synthesis and spectroscopic characterization of some lanthanide(III) nitrate complexes of ethyl 2-[2-(1-acetyl-2-oxopropyl)azo]-4,5-dimethyl-3-thiophenecarboxyate

Ethyl 2-[2-(1-acetyl-2-oxopropyl)azo]-4,5-dimethyl-3-thiophenecarboxyate was synthesized by coupling diazotized ethyl 2-amino-4,5-dimethylthiophene-3-carboxylate with acetylacetone. Based on various spectral studies and elemental analysis, an intramolecularly hydrogen-bonded azo-enol structural form was assigned for the ligand. This ligand is versatile in forming a series of lanthanide(III) complexes, viz., lanthanum(III), cerium(III), praseodymium(III), neodymium(III), samarium(III) and gadolinium(III), which were characterized through various spectral studies, elemental analysis, magnetic susceptibility measurements, molar conductance and thermal analysis. The spectral data revealed that the ligand acted as a neutral tridentate, coordinating to the metal ion through one of the azo nitrogen atoms, the ester carbonyl and the enolic oxygen of the acetylacetone moiety, without deprotonation. Molar conductance values adequately supported their non-electrolytic nature. The ligand and lanthanum(III) complex were subjected to X-ray diffraction studies. In addition, the lanthanum(III) complex underwent a facile transesterification reaction on refluxing with methanol for a long period. The thermal behaviour of the lanthanum(III) complex was also examined.