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.
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 conceptscatalysis inorganic chemistry Reactivity Relativistic DFT solvation