Characterization of Peroxo and Hydroperoxo Intermediates in the Aerobic Oxidation of N-Heterocyclic-Carbene-Coordinated Palladium(0)

An eta2-peroxopalladium(II) complex, derived from dioxygen addition to Pd(IMes)2 (IMes = bis-1,3-di(2,4,6-trimethylphenyl)imidazoline-2-ylidene), has been isolated and characterized. Subsequent addition of HOAc to (IMes)2Pd(O2) yields the first example of a hydroperoxopalladium species derived from molecular oxygen. The characterization and reactivity studies of these complexes provide the most detailed insights to date into the proposed mechanism for palladium(0) oxidation by molecular oxygen.