title: Oxygenation of simple zinc alkyls: surprising dependence of product distributions on the alkyl substituents and the presence of water.
abstract: 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.
authors.affiliation: Institut für Anorganische und Analytische Chemie, D-48149 Münster, Germany.
authors.forename: Surajit
authors.initials: S
authors.lastname: Jana
authors.forename: Raphael J F
authors.initials: RJ
authors.lastname: Berger
authors.forename: Roland
authors.initials: R
authors.lastname: Fröhlich
authors.forename: Tania
authors.initials: T
authors.lastname: Pape
authors.forename: Norbert W
authors.initials: NW
authors.lastname: Mitzel