Influence of Decreasing Solvent Polarity (Dioxane-Water Mixtures) on the Stability of Metal Ion Complexes Formed with Phosphate Monoesters

The acidity constants of H(R —M P)~, where R —MP: = 4-nitrophenyl phosphate (NPhP2 ). phenyl phosphate (PhP2 ) and D-ribose 5'-m onophosphate (RibM P2 ). and the stability constants of the binary C u (R -M P ) com plexes w'ere determined by potentiometric pH titrations in aqueous solution and in 20. 30, 40 and 50% (v/v) dioxane-water mixtures. The solvent influence on the corresponding equilibrium constants is compared with the same influence on previously studied systems containing uridine 5'-triphosphate. formate or acetate. The influence of the solvent composition on the various ligand (L) systems was evaluated by constructing log Km(L) versus pK[j(L) plots; in all cases straight lines are obtained with slopes close to 1. This indicates that in all these systems, despite the different negative charges of the involved ligands, the solvent effect on proton binding and on metal ion binding is approximately of the same size: A decreasing solvent polarity resulting from the addition of increasing amounts of organic solvent to the aqueous solutions favors the affinity of the negatively charged ligands for protons and metal ions as well. Information of this type is considered important because the ‘effective' or ‘equivalent solution' dielectric constants in active-site cavities of enzymes are reduced compared with the dielectric constant of bulk water; i. e., in protein cavities also a decreased ‘solvent polarity' is occurring and this is expected to affect the stability of metal ion-ligand bonds.