Our research group has made significant advances in understanding the reactivity of metal-carbon bond of group 12 and 13 organometallics, probing their activation toward dioxygen or sulfur (J. Am. Chem. Soc., 1996, 118, 6794; Chem. Eur. J., 2000, 6, 3215; J. Am. Chem. Soc., 2003, 125, 12698; Angew. Chem., Int. Ed., 2003, 42, 4643; Angew. Chem. Int. Ed., 2006, 45, 4826; Angew. Chem. Int. Ed., 2008, 47, 7888; Angew. Chem. Int. Ed., 2009, 48, 7017). Aside from any fundamental curiosity concerning the structure characterization of the first zinc alkylperoxides or novel zinc alkoxides and oxides, a plausible hypothesis concerning the reaction mechanism of zinc alkyls with O2 has been advanced (Scheme 1). Essentially all our new data are in contrast to the radical-chain mechanism, which has been widely accepted over decades but rather fails to explain the product formation in the oxygenation of zinc alkyls. We have also revealed a long overlooked decomposition pathway of zinc alkylperoxides via homolysis of the O-O bond. The generation of Zn oxyl and RO• radicals from homolysis of the ZnO-OR bond has been well-documented in the oxygenation of both dialkyl- and monoalkylzinc complexes.