Catalytically Active Iron(IV)oxo Species Based on a Bis(pyridinyl)phenanthrolinylmethane

Starting from the mononuclear iron(II) complex [Fe(MeCPy2Phen)(MeCN)2]2+, a non‐heme Fe(IV)oxo complex [FeIV(MeCPy2Phen)O]2+ was synthesized via oxidation with meta‐chloroperoxybenzoic acid (mCPBA). The Fe(IV)oxo complex was characterized using UV/Vis spectroscopy, Mößbauer spectroscopy and CSI mass...

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Bibliographic Details
Published in:Israel journal of chemistry 2020-10, Vol.60 (10-11), p.987-998
Main Authors: Hüppe, Henrika M., Keisers, Kristina, Fink, Fabian, Mürtz, Sonja D., Hoffmann, Alexander, Iffland, Linda, Apfel, Ulf‐Peter, Herres‐Pawlis, Sonja
Format: Article
Language:English
Subjects:
Bioinorganic Chemistry
Cyclohexane
C−H activation
Iron
Mass spectrometry
N ligands
Oxidation
Spectroscopy
Substrates
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Summary:Starting from the mononuclear iron(II) complex [Fe(MeCPy2Phen)(MeCN)2]2+, a non‐heme Fe(IV)oxo complex [FeIV(MeCPy2Phen)O]2+ was synthesized via oxidation with meta‐chloroperoxybenzoic acid (mCPBA). The Fe(IV)oxo complex was characterized using UV/Vis spectroscopy, Mößbauer spectroscopy and CSI mass spectrometry. The ability of this species to oxidize C−H bonds was tested with cyclohexane and adamantane as model substrates. For cyclohexane, an alcohol‐to‐ketone ratio (A/K) of 6.1 and efficiencies up to 55 were obtained. In case of adamantane, the ratio of tertiary over secondary products (3°/2°) is 38. In combination, this indicates the iron(IV)oxo complex being the catalytically active species.
ISSN:0021-2148
1869-5868
DOI:10.1002/ijch.202000009