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Inorg Chem. 2007 May 14;46(10):4293-7. Epub 2007 Apr 7.

Oxygenation of simple zinc alkyls: surprising dependence of product distributions on the alkyl substituents and the presence of water.

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Institut für Anorganische und Analytische Chemie, D-48149 Münster, Germany.


Oxygenation reactions of dialkylzinc solutions have been investigated. Me2Zn reacts with oxygen in the absence of water to give the bis(heterocubane) [(MeZn)6Zn(OMe)8], whereas Et2Zn and iPr2Zn 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)6Zn(OEt)8], while being retained for iPr2Zn (giving [(iPrZn)4(OiPr)4]). Full characterization of all products by NMR spectroscopy, mass spectrometry, and elemental analyses is provided, and crystal structures of [(EtZn)6Zn(OEt)8] and [(iPrZn)4(OiPr)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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