Equilibria and kinetics for pH-dependent axial ligation of alkyl(aquo) cobaloximes with aromatic and aliphatic N-donor ligands

Equilibria and kinetics of the reaction of bromomethyl(aquo) cobaloxime with histamine, histidine, glycine and ethyl glycine ester and iodomethyl(aquo) cobaloxime with cyanide, imidazole and substituted imidazoles were studied as a function of pH at 25C, 1,0 M ionic strength (KCl) by spectrophotometry technique. The rate of substitution of H2O varies with the pKa of the incoming ligand, thus establishing the existence of nucleophilic participation of the ligand in the transition state. Dissociation kinetic reactions were also studied as a function of pH. Binding and kinetic data were interpreted based on the basicity, steric crowd of the entering ligand and HSAB principle. To compare the rate constants of the entering ligands pH independent second-order rate constants were calculated.