Formation of Mixed-Ligand Complexes of Pd(2+) with Nucleoside 5'-Monophosphates and Some Metal-Ion-Binding Nucleoside Surrogates

Formation of mixed-ligand Pd(2+) complexes between canonical nucleoside 5'-monophosphates and five metal-ion-binding nucleoside analogs has been studied by (1)H-NMR spectroscopy to test the ability of these nucleoside surrogates to discriminate between unmodified nucleobases by Pd(2+)-mediated base pairing. The nucleoside analogs studied included 2,6-bis(3,5-dimethylpyrazol-1-yl)-, 2,6-bis(1-methylhydrazinyl)- and 6-(3,5-dimethylpyrazol-1-yl)-substituted 9-(β-d-ribofuranosyl)purines 1–3, and 2,4-bis(3,5-dimethylpyrazol-1-yl)- and 2,4-bis(1-methylhydrazinyl)-substituted 5-(β-d-ribofuranosyl)-pyrimidines 4–5. Among these, the purine derivatives 1-3 bound Pd(2+) much more tightly than the pyrimidine derivatives 4, 5 despite apparently similar structures of the potential coordination sites. Compounds 1 and 2 formed markedly stable mixed-ligand Pd(2+) complexes with UMP and GMP, UMP binding favored by 1 and GMP by 2. With 3, formation of mixed-ligand complexes was retarded by binding of two molecules of 3 to Pd(2+).