Complexing of 3d transition metal ions with 9-substituted purines. IV. The effect of base-stacking on the basicity and complexing-ability

A number of 9-methylpurines were equilibrated between carbon tetrachloride or chloroform and aqueous solutions containing either nickel(II) perchlorate or N⁶,N⁶-dimethyladenosine. The equilibrium constants for the complex formation with nickel(II) ion and association with N⁶,N⁶-dimethyladenosine were calculated on the basis of the distribution data. The results, together with those obtained in the presence of both nickel(II) perchlorate and N⁶,N⁶-dimethyladenosine, are interpreted to indicate that stacking-association with the latter compound reduces the complexing-ability of 9-methylpurines. The protonation of guanosine in the presence of caffeine was examined potentiostatically and its association with caffeine studied by phase-solubility measurements. Association with caffeine was shown to lower the basicity of guanosine.