title: O2 Activation and Double C-H Oxidation by a Mononuclear Manganese(II) Complex.
abstract: A Mn(II) complex, [Mn(dpeo)2](2+) (dpeo=1,2-di(pyridin-2-yl)ethanone oxime), activates O2, with ensuing stepwise oxidation of the methylene group in the ligands providing an alkoxide and ultimately a ketone group. X-ray crystal-structure analysis of an intermediate homoleptic alkoxide Mn(III) complex shows tridentate binding of the ligand via the two pyridyl groups and the newly installed alkoxide moiety, with the oxime group no longer coordinated. The structure of a Mn(II) complex of the final ketone ligand, cis-[MnBr2(hidpe)2] (hidpe=2-(hydroxyimino)-1,2-di(pyridine-2-yl)ethanone) shows that bidentate oxime/pyridine coordination has been resumed. H2(18)O and (18)O2 labeling experiments suggest that the inserted O atoms originate from two different O2 molecules. The progress of the oxygenation was monitored through changes in the resonance-enhanced Raman bands of the oxime unit.
authors.affiliation: Department of Physics, Chemistry and Pharmacy, University of Southern Denmark, Campusvej 55, 5230 Odense M (Denmark).
authors.forename: Claire
authors.initials: C
authors.lastname: Deville
authors.affiliation: Molecular Inorganic Chemistry, Stratingh Institute for Chemistry, University of Groningen, Nijenborgh 4, 9747 AG Groningen (The Netherlands).
authors.forename: Sandeep K
authors.initials: SK
authors.lastname: Padamati
authors.affiliation: Department of Physics, Chemistry and Pharmacy, University of Southern Denmark, Campusvej 55, 5230 Odense M (Denmark).
authors.forename: Jonas
authors.initials: J
authors.lastname: Sundberg
authors.affiliation: Department of Physics, Chemistry and Pharmacy, University of Southern Denmark, Campusvej 55, 5230 Odense M (Denmark).
authors.forename: Vickie
authors.initials: V
authors.lastname: McKee
authors.affiliation: Molecular Inorganic Chemistry, Stratingh Institute for Chemistry, University of Groningen, Nijenborgh 4, 9747 AG Groningen (The Netherlands).
authors.forename: Wesley R
authors.initials: WR
authors.lastname: Browne
authors.affiliation: Department of Physics, Chemistry and Pharmacy, University of Southern Denmark, Campusvej 55, 5230 Odense M (Denmark). mckenzie@sdu.dk.
authors.forename: Christine J
authors.initials: CJ
authors.lastname: McKenzie
keywords: CH oxidation; O2 activation; catalysis; manganese; oxime ligands