Metal-catalyzed oxidations, 10 - New insights into the mechanism of hydroperoxide activation by investigation of dynamic processes in the coordination sphere of seven-coordinated molybdenum peroxo complexes

Seven-coordinated molybdenum oxobisperoxo complexes with chelate nitrogen d onors like pyrazolylpyridines are catalysts for the epoxidation of olefins. An NMR spectroscopic and quantumchemical study on the fluxionality of the chelate Ligand proves that during this process partial Ligand dissociation takes place. This gave rise to a detailed theoretical study on the activati on of CH3OOH at the model complex (NH3)(2)MoO(O-2)(2) including dissociatio n of one of the ammonia ligands and proton transfer from the hydroperoxide to one of the peroxo ligands.