Voltammetric, Potentiometric and Spectrophotometric Studies of Some Hydrazones and Their Metal Complexes in Ethanolic-Aqueous Buffered Solutions

Summary.

The electrochemical behavior of some hydrazones derived from 6-chloro-2-hydrazinopyridine in the Britton-Robinson universal buffer of pH 2–11 containing 35% ethanol was investigated at the mercury electrode using dc-polarography, controlled-potential coulometry, and cyclic voltammetry techniques. The examined hydrazones were reduced in solutions of pH < 9 in a single 4-electron diffusion-controlled irreversible step corresponding to both the saturation of –N=C< double bond and cleavage of the –HN–NH– single bond of the hydrazone molecule via the consumption of two electrons for each center. Whereas the starting compound, 6-chloro-2-hydrazinopyridine, was reduced in a single 2-electron diffusion-controlled irreversible step corresponding to cleavage of its –NH–NH₂ single bond. The mechanistic pathway of the electrode reaction of the studied compounds was elucidated and discussed. The pK _a values of the examined hydrazones and the stoichiometry of their complexes in solution with some transition metal ions were determined spectrophotometrically. The dissociation constants and the thermodynamic parameters of the investigated hydrazones, and the stability constants of their metal complexes in solution were determined potentiometrically.