Premium
O 2 Activation and Double CH Oxidation by a Mononuclear Manganese(II) Complex
Author(s) -
Deville Claire,
Padamati Sandeep K.,
Sundberg Jonas,
McKee Vickie,
Browne Wesley R.,
McKenzie Christine J.
Publication year - 2016
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201508372
Subject(s) - chemistry , oxime , alkoxide , homoleptic , ketone , ligand (biochemistry) , denticity , pyridine , methylene , manganese , medicinal chemistry , moiety , crystal structure , stereochemistry , crystallography , catalysis , organic chemistry , metal , biochemistry , receptor
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.