Synthesis of bilaterally thiadiazole substituted vic-dioxime ligands and investigation of their polymeric metal complexes

Abstract

In this study, three novels substituted 1,3,4-thiadiazole-derived vic-dioxime ligands and their corresponding polymeric transition metal (Co2+and Ni2+) complexes were synthesized and their structural characterizations were performed. For this purpose, 4,4′-bis(chloroacetyldiphenyl) ether (OKS1) was obtained from the reaction of diphenyl ether with chloroacetyl chloride at a 1:2 molar ratio with the help of the Friedel-Crafts reaction. Our first starting oxime compound “2,2′-(oxybis(4,1-phenylene))bis(N‑hydroxy-2-oxoacetimidoyl) chloride (OKS2)” was obtained from the reaction of OKS1 with butyl nitrite at a 1:2 molar ratio under the catalysis of HCl gas. Then, our final starting vic-dioxime compound “2,2′-(oxybis(4,1-phenylene))bis(N‑hydroxy-2-(hydroxyimino) acetimidoyl) chloride (OKS3)” was obtained from the reaction of OKS2 with hydroxylamine hydrochloride in ethanol media at 40 °C. Then, our three original target vic-dioxime compounds (OKL1-OKL3) were synthesized from the reaction of substituted 2-amino-1,3,4-thiadiazole compounds with OKS3. Structural characterizations of all synthesized organic compounds were made using elemental analysis, FTIR, 1H and 13C NMR and mass spectroscopy methods. Target complexes were obtained from the reaction of all ligands with MCl2.nH2O (M: Co2+and Ni2+) salts, and their structures were elucidated using FTIR, magnetic susceptibility, thermogravimetric analysis, elemental analysis, and ICP-OES spectroscopy methods.