MOF-Stabilized Perfluorinated Palladium Cages Catalyze the Additive-Free Aerobic Oxidation of Aliphatic Alcohols to Acids

Extremely high electrophilic metal complexes, composed by a metal cation and very electron poor σ-donor ancillary ligands, are expected to be privileged catalysts for oxidation reactions in organic chemistry. However, their low lifetime prevents any use in catalysis. Here we show the synthesis of fluorinated pyridine-Pd coordinate cages within the channels of an anionic tridimensional metal-organic framework (MOF), and their use as efficient metal catalysts for the aerobic oxidation of aliphatic alcohols to carboxylic acids without any additive. Mechanistic studies strongly support that the MOF-stabilized coordination cage with perfluorinated ligands unleashes the full electrophilic potenti…