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MOF–stabilized perfluorinated palladium cages catalyze the additive–free aerobic oxidation of aliphatic alcohols to acids

DOI: 10.1002/chem.202103781 DOI Help

Authors: Rossella Greco (CSIC, ITQ) , Estefanía Tiburcio-Fortes (Universidad de Valencia) , Antonio Fernandez (Loughborough University) , Carlo Marini (ALBA Synchrotron) , Alejandro Vidal-Moya (CSIC, ITQ) , Judit Oliver-Meseguer (CSIC, ITQ) , Donatella Armentano (Universita della Calabria) , Emilio Pardo (Universidad de Valencia) , Jesus Ferrando-Soria (Universitat de Valencia) , Antonio Leyva-Perez (CSIC, ITQ)
Co-authored by industrial partner: No

Type: Journal Paper
Journal: Chemistry – A European Journal

State: Published (Approved)
Published: December 2021
Diamond Proposal Number(s): 22411

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 O 2 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.

Journal Keywords: per–fluorinated palladium complexes; metal-organic frameworks; supramolecular coordination cages; aerobic alcohol oxidation to carboxylic acid; single crystal X–Ray diffraction

Subject Areas: Chemistry, Materials

Instruments: I19-Small Molecule Single Crystal Diffraction

Added On: 21/12/2021 15:57

Discipline Tags:

Physical Chemistry Catalysis Chemistry Materials Science Metal-Organic Frameworks Metallurgy Organometallic Chemistry

Technical Tags:

Diffraction Single Crystal X-ray Diffraction (SXRD)