Kinetics and mechanism of aqua ligand substitution reactions from cis-diaqua-bis(bipyridine)ruthenium(II) ion by pyridine-2-aldoxime in aqueous medium

Abstract

The kinetic behaviour of cis-[Ru(bipy)2(H2O)2]2+ towards the anating ligand pyridine-2-aldoxime as a function of temperature, ligand concentration, substrate complex concentration and pH is reported and the rate expression Rate = k1k2[Ru(bipy)2(H2O)2]2+ [LL]/(k-1 + k2[LL]) is established where k1 is the water dissociation rate constant for the slow step, k-1 is the rate constant for the aquation, k2 is the ligand-capturing rate constant of the five-coordinate intermediate [Ru(bipy)2(H2O)]2+ and LL is pyridine-2-aldoxime. The reaction is pH-dependent in the pH range 3.65–5.50. The enthalpy and entropy of activation were obtained using Eyring plots. The results are in conformity with a dissociative mechanism.