Unprecedented Water Addition to the ,β-Unsaturated Enone Bond, Mediated by the Combination of Carbonate and Platinum(II)

摘要

The cytostatic compounds cis-[Pt(A9pyp)(dmso)Cl₂] (1) and [Pt(A9pyp)(dmso)(cbdca)] (2) (A9pyp=(E)-[1-(9-anthryl)-3-(2-pyridyl)-2-propenone) as carrier ligand; cbdca=cyclobutane dicarboxylate) have been found to add water across the enone CC bond of the ligand A9pyp. The water addition occurs in the presence of carbonate buffer, and has been followed in detail using NMR and ESI-MS spectroscopy. The spectroscopic data clearly indicate that the platinum(II) ion, the carbonate species, and the proximity of the enone CC bond to the metal ion, are all required for this unusual hydration. A difference in kinetics is observed between chloride and cbdca, showing that the Pt–ligand dissociation plays an important role in the hydration kinetics.