New Pyrazole-Based Ligands: Synthesis, Characterization, and Catalytic Activity of Their Copper Complexes

The purpose of this study is to demonstrate the synthesis of pyrazole-based ligands and to evaluate their catalytic properties in the oxidation reaction of catechol to o-quinone. The ligands were prepared via the condensation of (3,5-dimethyl-1H pyrazol-1-yl)methanol A with the appropriate primary amine. Four pyrazole-based ligands were successfully synthesized and characterized. These ligands provide one pyrazole sp2-nitrogen, one pyridine sp2-nitrogen, and one amine sp3-nitrogen, which were capable of coordinating to the metal. For evaluating the catalytic activity, the experiments were tested by varying the type of solvent, metal ion, anion in the metal salt, and ratios of ligands and metal salts. Excellent catalytic activities for the oxidation of catechol to o-quinone were obtained. The copper (II)-based complexes showed better reactions rates than those based on other metals (e.g., nickel, tin, and barium), which was due to the fact that the active catalytic site of the catecholase enzyme has two active sites from the existence of copper (II) ions. The composition ratios of ligands and metal salts as well as the type of anion in the metal salt bring impacts to the formation of complexes. We found also that the type of solvent contributes to the interaction and dilution of reactants in the solvent. This study demonstrated that the present ligands can be used as a model for further developments in catalytic processes relating to catecholase activity.