MOF‐Stabilized Perfluorinated Palladium Cages Catalyze the Additive‐Free Aerobic Oxidation of Aliphatic Alcohols to Acids. Issue 7 (12th January 2022)

• Record Type: Journal Article
• Authors: Greco, Rossella; Tiburcio‐Fortes, Estefania; Fernandez, Antonio; Marini, Carlo; Vidal‐Moya, Alejandro; Oliver‐Meseguer, Judit; Armentano, Donatella; Pardo, Emilio; Ferrando‐Soria, Jesús; Leyva‐Pérez, Antonio
• Is Part Of: Chemistry. Volume 28:Issue 7(2022)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2022-01-12
• Subjects: aerobic alcohol oxidation to carboxylic acid -- metal-organic frameworks -- per-fluorinated palladium complexes -- single-crystal X-Ray diffraction -- supramolecular coordination cages; Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.202103781
• Languages: English
• ISSNs: 0947-6539

Abstract

Abstract: 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 2+ 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 2+ to dehydrogenate primary alcohols, without any base, and also to activate O2 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. Abstract : Fluorinated pyridine‐Pd 2+ coordinate cages have been synthesized and characterized with atomic resolution within the channels of a metal‐organic framework (MOF), and used as catalysts during the aerobic oxidation of aliphatic alcohols to carboxylic acids without any additive. These results illustrate a rare example of stable per‐fluorinated cationic metal complex, with potential implications in the future design of catalytic organometallic complexes.