Fei H, Sin J, Meng YS, Adelhardt M, Sutter J, Meyer K, Cohen SM * University of California,
San Diego, USA and Friedrich-Alexander-Universität Erlangen-Nürnberg, Germany
Reusable Oxidation Catalysis Using Metal-Monocatecholato Species in a Robust Metal-Organic
Framework.
J. Am. Chem. Soc. 2014;
136: 4965-4973
Key words
metal-organic framework - chromium-monocatecholato moieties - oxidation - heterogeneous
catalysis
Significance
The metal-organic framework 1, UiO-66-CrCAT, was prepared from zirconium(IV)-based UiO-66 (UiO = University of
Oslo) and aqueous K2CrO4 under acidic conditions of pH 3. The oxidation reaction of secondary alcohols was
carried out with TBHP in the presence of UiO-66-CrCAT (1 mol% chromium) in chlorobenzene
(method A) or under solvent-free conditions (method B) to afford the corresponding
ketones.
Comment
The catalyst was characterized by SEM, XPS, X-ray absorption near-edge structure (XANES)
and extended X-ray absorption fine structure (EXAFS) spectroscopy, BET, XRD, and
ICP-OES analyses. The catalyst was recovered by filtration and reused four times without
significant loss of the catalytic activity and without leaching of chromium from the
catalyst in the oxidation of 2-heptanol. Further, reactions of sec-benzylic alcohols proceeded with H2O2 in acetonitrile (method C).
