Catalytic oxygenation by Ruthenium Polyoxometalates
The catalytic oxydation of DMSO has been established with ruthenium polyoxometalates (POMs). The catalytic cycle has been revealed through a combination of experiments and theory, with the key intermediate established by relativistic DFT calculations as a POM-dimer with a Ru(IV)-μ-peroxo-Ru(IV) bridge.
Catalytic cycle for DMSO oxidation by Ru-POMs, with in the middle the HOMO of the Ru(IV)-μ-peroxo-Ru(IV) bridge, the key intermediate.
The paper was highlighted on the back cover of Chemistry a European Journal.
relativistic DFT, COSMO solvation, catalysis
A. Sartorel, P. Miró, M. Carraro, S. Berardi, O. Bortolini, A. Bagno, C. Bo, and M. Bonchio, Oxygenation by Ruthenium Monosubstituted Polyoxotungstates in Aqueous Solution: Experimental and Computational Dissectionof a Ru(III)–Ru(V) Catalytic Cycle, Chem. Eur. J. 20, 10932-10943 (2014).
Key conceptsADF catalysis inorganic chemistry Reactivity Relativistic DFT solvation