Molybdenum-Oxo and Peroxo Complexes in Oxygen Atom Transfer Processes with O2 as the Primary Oxidant

The chemistry of Oxygen Atom Transfer catalyzed by metal-dioxo and metal-oxo-peroxo complexes, described in this mini review is limited to processes in which the primary oxidant is dioxygen. Contrary to the vast majority of OAT catalytic systems reported in the literature and involving oxidant such as hydroperoxide, peracid, hydrogen peroxide, DMSO or N2O, the use of dioxygen is certainly more arduous since it brings up more constraints. First, experimental conditions must minimize free radical chain pathways in order to avoid unselective product formation. Second, it is essential that the catalytic system be able , not only, to activate O2 but also transfer both oxygen atoms to a substrate. Examples from the literature and from our laboratory are given for systems under homogeneous conditions and with recently reported more performant solid matrix anchored catalysts.