6533b7d9fe1ef96bd126c2ef
RESEARCH PRODUCT
MOF-Stabilized Perfluorinated Palladium Cages Catalyze the Additive-Free Aerobic Oxidation of Aliphatic Alcohols to Acids
Rossella GrecoEstefania Tiburcio‐fortesAntonio FernandezCarlo MariniAlejandro Vidal-moyaJudit Oliver-meseguerDonatella ArmentanoEmilio PardoJesús Ferrando-soriaAntonio Leyva‐pérezsubject
Organic ChemistryGeneral ChemistryCatalysisdescription
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 potential of Pd to dehydrogenate primary alcohols, without any base, and also to activate O for the radical oxidation to the aldehyde intermediate. This study opens the door to design catalytic perfluorinated complexes for challenging organic transformations, where an extremely high electrophilic metal site is required.
| year | journal | country | edition | language |
|---|---|---|---|---|
| 2021-10-20 |