Issue 24, 2006

Molecular oxygen and oxidation catalysis by phosphovanadomolybdates

Abstract

The history of aerobic catalytic oxidation mediated by a subclass of polyoxometalates, the phosphovanadomolybdates of the Keggin structure, [PVxMo12−xO40](3+x)−, is described. In the earlier research it was shown that phosphovanadomolybdates catalyze oxydehydrogenation reactions through an electron-transfer oxidation of a substrate by the polyoxometalate that is then reoxidized by oxygen. These aerobic oxidations are selective and synthetically useful in various transformations, notably diene aromatization, phenol dimerization and alcohol oxidation. Oxygen transfer from the polyoxometalate to arenes and alkylarenes was also discussed as a homogeneous analog of a Mars–van Krevelen oxidation. “Second generation” catalysts include binary complexes of the polyoxometalate and a organometallic compound useful, for example, for methane oxidation and nanoparticles stabilized by polyoxometalates effective for aerobic alkene epoxidation.

Graphical abstract: Molecular oxygen and oxidation catalysis by phosphovanadomolybdates

Article information

Article type
Feature Article
Submitted
17 Jan 2006
Accepted
06 Mar 2006
First published
17 Mar 2006

Chem. Commun., 2006, 2529-2538

Molecular oxygen and oxidation catalysis by phosphovanadomolybdates

R. Neumann and A. M. Khenkin, Chem. Commun., 2006, 2529 DOI: 10.1039/B600711M

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