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The following equilibrium constants (given as logK in units of m(-1)) were determined for the substitution of co-ordinated H(2)O in aquocobalamin by glycine (bound through N) 5.8, cysteine (bound through S) 6.0 or 8.3, depending on the value chosen for the pK of the thiol group, and phenolate 2.9. The spectrum of the phenolate cobalamin shows an additional intense absorption band at 468nm with a molar extinction coefficient of 1.1x10(4), which is assigned to a charge transfer from the phenolate to the cobalt ion. Equilibrium constants have also been determined for the equilibria between adenylcobamide cyanide and CN(-), HO(-) and H(+), which show that the adenine is more easily displaced by CN(-) and HO(-) than is 5,6-dimethylbenziminazole in vitamin B(12), but can be protonated by acid while still remaining co-ordinated to the cobalt. It is shown that in the binding of corrinoids to proteins and polypeptides the formation of hydrogen bonds is far more important than co-ordination by the metal.