O2 Activation and Double CH Oxidation by a Mononuclear Manganese(II) Complex. (3rd December 2015)

• Record Type: Journal Article
• Authors: Deville, Claire; Padamati, Sandeep K.; Sundberg, Jonas; McKee, Vickie; Browne, Wesley R.; McKenzie, Christine J.
• Is Part Of: Angewandte Chemie. Volume 128:Number 2(2016)
• Page Start: 555
• Page End: 559
• Publication Date: 2015-12-03
• Subjects: C‐H‐Oxidation -- Katalyse -- Mangan -- O2‐Aktivierung -- Oxim‐Liganden; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.201508372
• Languages: English
• ISSNs: 0044-8249

Abstract

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.