An Air-Stable Molybdenum-Based Precatalyst in Oxygen-Atom Transfer Reactions
Résumé
We report on the preparation and characterization of two new air‐stable mononuclear molybdenum(VI) complexes, termed MoVIO2(OPNO)2 (1) and MoVIO2(SPNO)2 (2). The potential of these complexes to act as functional mimics of molybdoenzymes from the DMSO reductase family was investigated. Initial catalytic studies suggest that 2 (but not 1) catalyzes the reduction of a sulfoxide into the thioether derivative. Studying the catalytic intermediates by UV/Vis spectroscopy, NMR spectroscopy, and DFT indicates that the active species (SPNO)2OMoV–O–MoVO(SPNO)2 (4), a dinuclear molybdenum(V) dimer with one µ‐oxo bridge, is formed upon successive reduction of the (SPNO)– ligands and the molybdenum(VI) ion.