Details

Autor(en) / Beteiligte

• Deville, Claire
• Padamati, Sandeep K
• Sundberg, Jonas
• McKee, Vickie
• Browne, Wesley R
• McKenzie, Christine J

Titel

O2 Activation and Double CH Oxidation by a Mononuclear Manganese(II) Complex

Ist Teil von

• Angewandte Chemie International Edition, 2016-01, Vol.55 (2), p.545

Auflage

International ed. in English

Ort / Verlag

Weinheim: Wiley Subscription Services, Inc

Erscheinungsjahr

2016

Quelle

Alma/SFX Local Collection

Beschreibungen/Notizen

• A MnII 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 MnIII 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 MnII 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. H218O and 18O2 labeling experiments suggest that the inserted Oatoms 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.