Equilibria of the axial ligation of benzyl(aquo)cobaloximes by imidazole, 1-methyl imidazole, histidine, histamine, glycine, ethyl glycine ester, thiourea and urea have been spectrophotometrically measured in aqueous solutions of ionic strength 1.0M (KCl) at 25°C as a function of pH. The equilibrium constants are in the order CN⁻> 1-methyl imidazole > imidazole > histidine > histamine>glycine>ethyl glycine ester > thiourea > urea. The order of stability of benzyl(ligand)cobaloxime is explained based on the basicity of the ligand, Co(III) →>L dπ- pπback bonding and soft-soft and soft-hard interaction. Imidazole, substituted imidazoles, histidine and histamine form more stable complexes than glycine, ethyl glycine ester in contrast to the basicity of the ligands. Benzyl(ligand)cobaloximes were isolated and characterized by elemental analysis, IR and¹H NMR spectra.

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 ofpH at 25°C, 10 M ionic strength (KCl) by spectrophotometry technique. The rate of substitution of H₂O varies with thepKa 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 ofpH. 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 ligandspH independent second-order rate constants were calculated.

Kinetics and equilibria of axial ligation of bromomethyl(aquo) cobaloxime by a series of straight chain primary amines (methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine), cycloamines (cyclopentylamine, cyclohexylamine, cycloheptylamine) and secondary amines (N,N-dimethylamine, N,N-diethylamine) have been measured as functions of pH by spectrophotometric technique in aqueous solution, ionic strength 1 M (KCl) at 25°C. The rate of substitution of H₂O varies with the pKa of incoming ligand, thus establishing nucleophilic participation of the ligand in the transition state. Binding and kinetic data are interpreted based on the basicity and steric influence of the entering ligand. To compare the rate constants of the entering ligands, pH independent second-order rate constants (k_on) are calculated.

Equilibria and kinetics of the reactions of chloromethyl(aquo)cobaloxime with histamine, histidine, glycine and ethyl glycine ester were studied as a function of pH at 25°C, 10 M ionic strength (KCl) by spectrophotometric techniques. Comparison of equilibrium constants and rate constants tells that the order isK_Hisdn >K_Hiamn >K_Gly >K_EtGlyest. The rate of substitution of H₂O varies with the pKa of the incoming ligand and nucleophilic participation of the ligand in the transition state. The rate constants and equilibrium constants are correlated to the hardness and softness of the ligands and the Co(III) of cobaloxime.

Equilibrium constants are determined for the reaction of ethylester and methyl ester (aquo) cobaloximes with histamine, histidine, glycine and ethyl glycine ester as a function of pH at 25°C, using spectrophotometric technique. The functional dependence of pK_a on the substitution rate of H₂O varies with the pK_a of the incoming ligand, establishing the existence of nucleophilic participation of the ligand in the transition state. This data is interpreted with the help of kinetic data where dissociation kinetic reactions were also studied as a function of pH. Binding and kinetic data were correlated based on the basicity, steric hindrance of the entering ligand and HSAB principle. To compare the rate constants of the entering ligands pH-independent second-order rate constants were calculated. The effect of incoming ligand on Co-C bond is studied using molecular mechanics

Substitution reactions of propyl cobaloxime with imidazole, substituted imidazoles, histidine, histamine, glycine and ethyl glycine ester are carried out as a function of pH. Trends in the formation constants are explained based on the steric hindrance, extent of π-bonding and Σ-donor capacity of the incoming ligand. Molecular mechanics is used to theoretically determine the bond length and bond strain values by MM2 parametrization and these are correlated with the experimental data.

Spectroscopic characterization (IR, NMR and electronic spectra) of methyl (ligand) cobaloxime was done, where ligand = pyrazole, dimethyl pyrazole, alanine and alanine methyl ester. The frequency changes in the IR spectra and shifts in the NMR were explained on the basis of basicity of the ligand, steric hindrance, HSAB principle and $d\pi-p\pi$ back-bonding from metal to ligand. Alanine and alanine methyl ester form more stable complexes than pyrazole and dimethyl pyrazole. Based on their IR and ¹H NMR spectra it is inferred that pyrazole and dimethylpyrazole bind to Co (III) via N-2 ring nitrogen, i.e. monodentate coordination.

The kinetics and equilibria for the axial ligation of pyridine and substituted pyridines to bromomethyl(aqua)cobaloxime have been measured spectrophotometrically in aqueous solutions of ionic strength 1.0 M (KC1) at 25°C as a function of 𝑝H. The binding constants and rate of formation increase in the order 4-NH₂Py 4-EtPy > 4-MePy > Py > 2-NH₂Py > 2-EtPy. The data have been interpreted based on the basicity of the ligand, 𝜋-back bonding from Co(III) → L and hard and soft interactions. 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. We have investigated the DNA binding of bromomethyl(aqua)cobaloxime with DNA. Bromomethyl(ligand)cobaloximes were isolated and characterized by elemental analysis, IR and NMR (¹H, ¹³C) spectra.