Organo-Polyoxometalate-Based Hydrogen-Bond Catalysis

Several urea-inserted organo-polyoxometalates (POMs) derived from polyoxotungstovanadate [P2V3W15O61]9− were prepared. The insertion of the carbonyl into the polyoxometallic framework activates the urea toward Hydrogen-bond catalysis. This was shown on the Friedel-Crafts arylation of trans-β-nitrostyrene. Modelling shows that the most stable form of the organo-POMs features a cis-trans arrangement of the two N−H bonds, but that the likely catalytically active trans-trans form is accessible at room temperature. Finally, it is possible that the oxo substituents next to the vanadium atoms may help the approach of the nucleophile via H-bonding.