Coenzyme B12 model studies: An HSAB approach to the equilibria and kinetics of axial ligation of alkyl(aquo)- cobaloximes by imidazole and cyanide

Kinetics and equilibria of the axial ligation of alkyl(aquo)cobaloximes by imidazole and cyanide have been measured spectrophotometrically in aqueous solutions of ionic strength 10 M at 25C as a function of pH. Comparison of KIMD and KCN– of CH3, C2H5 and BrCH2 cobaloximes indicates that their stability is in the order BrCH2 > CH3 > C2H5. As the electron-withdrawing capacity of the alkyl group trans to water increases, the electron density of the cobalt(III) decreases and thus it becomes a stronger Lewis acid and binds more strongly to imidazole and cyanide. The association and dissociation rate constants are better correlated to the relative softness of the ligand showing that cyanide binds 30 times faster than imidazole. These complexes are isolated and are characterized by IR and 1H NMR spectra.