Abstract
Equilibrium constants for substitution of Cl − by cytidine in PdCl 4 2− and Pd(en)Cl 2 in aqueous solution were determined. Equilibrium constants for substitution of Cl − by pyridine in Pd(en)Cl 2 were also measured. For unit ionic strength at 25°C, log K values for the successive substitutions of two chlorides are: PdCl 4 2− -cytidine, log K 1 = 4.49, log K 2 = 3.45; Pd(en)Cl 2-cytidine, log K 1 = 3.32, log K 2 = 2.56; Pd(en)Cl 2-pyridine, log K 1 = 4.31, log K 2 = 3.15. Comparison of equilibrium constants indicates that intramolecular hydrogen bonding and steric interactions of the exocyclic substituents ortho to the binding site of cytidine do not contribute significantly to the stability of the palladium-nucleoside complexes. Coordination equilibria, of deprotonated cytidine occur in alkaline solutions of PdCl 4 2− and the ligand.
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