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| - Trinuclear Copper(II) Complex Showing High Selectivity forthe Hydrolysis of 2‘−5‘ over 3‘−5‘ for UpU and3‘−5‘ over 2‘−5‘ for ApA Ribonucleotides
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| - The cooperative action of multiple Cu(II) nuclear centers is shown to be effective and selectivein the hydrolysis of 2‘−5‘ and 3‘−5‘ ribonucleotides. Reported herein is the specific catalysis by two trinuclearCu(II) complexes of L3A and L3B. Pseudo first-order kinetic studies reveal that the L3A trinuclear Cu(II)complex effects hydrolysis of Up(2‘−5‘)U with a rate constant of 28 × 10-4 min-1 and Up(3‘−5‘)U with arate constant of 0.5 × 10-4 min-1. The hydrolyses of Ap(3‘−5‘)A and Ap(2‘−5‘)A proceed with rate constantsof 24 × 10-4 min-1 and 0.5 × 10-4 min-1 respectively. The L3A trinuclear Cu(II) complex demonstrateshigh specificity for Up(2‘−5‘)U and Ap(3‘−5‘)A. Similar studies with the more rigid L3B trinuclear Cu(II)complex shows no selectivity and yields lower rate constants for hydrolysis. The selectivity observed withthe L3A ligand is attributed to the geometry of the ligand-bound diribonucleotide which ultimately dictatesthe proximity of the attacking hydroxyl and the phosphoester to a Cu(II) center for activation and subsequenthydrolysis.
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