Oxygenation reactions of dialkylzinc solutions have been investigated. Me2Zn reacts with oxygen in the absence of water to give the bis(heterocubane) [(MeZn)(6)Zn(OMe)(8)], whereas Et2Zn and (Pr2Zn)-Pr-i afford the mono(heterocubanes) [(RZn)(4)(OR)(4)]. In the presence of small amounts of water (added during or after the oxygenation) the product types are reversed for Me2Zn and Et2Zn giving [(MeZn)(4)(OMe)(4)] and [(EtZn)(6)Zn(OEt)(8)], while being retained for (Pr2Zn)-Pr-i (giving [((PrZn)-Pr-i)(4)((OPr)-Pr-i)(4)]). Full characterization of all products by NMR spectroscopy, mass spectrometry, and elemental analyses is provided, and crystal structures of [(EtZn)(6)Zn(OEt)(8)] and [((PrZn)-Pr-i)(4)((OPr)-Pr-i)(4)] are reported. A rationalization of the different reactivities is attempted on the basis of DFT-calculated energies of some key reactants.
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