O 2 Activation and Double CH Oxidation by a Mononuclear Manganese(II) Complex

A Mn II complex, [Mn(dpeo) 2 ] 2+ (dpeo=1,2‐di(pyridin‐2‐yl)ethanone oxime), activates O 2 , 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 compl...

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Published in:Angewandte Chemie International Edition 2016-01, Vol.55 (2), p.545-549
Main Authors: Deville, Claire, Padamati, Sandeep K., Sundberg, Jonas, McKee, Vickie, Browne, Wesley R., McKenzie, Christine J.
Format: Article
Language:English
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Summary:A Mn II complex, [Mn(dpeo) 2 ] 2+ (dpeo=1,2‐di(pyridin‐2‐yl)ethanone oxime), activates O 2 , 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 ‐[MnBr 2 (hidpe) 2 ] (hidpe=2‐(hydroxyimino)‐1,2‐di(pyridine‐2‐yl)ethanone) shows that bidentate oxime/pyridine coordination has been resumed. H 2 18 O and 18 O 2 labeling experiments suggest that the inserted O atoms originate from two different O 2 molecules. The progress of the oxygenation was monitored through changes in the resonance‐enhanced Raman bands of the oxime unit.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.201508372