New Example of a Non-Heme Mononuclear Iron(IV) Oxo Complex. Spectroscopic Data and Oxidation Activity

The green complex S = 1 [(TPEN)FeO]2+ [TPEN = N,N,N‘,N‘-tetrakis(2-pyridylmethyl)ethane-1,2-diamine] has been obtained by treating the [(TPEN)Fe]2+ precursor with meta-chloroperoxybenzoic acid (m-CPBA). This high-valent complex belongs to the emerging family of synthetic models of FeIVO intermediat...

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Bibliographic Details
Published in:Inorganic chemistry 2005-12, Vol.44 (25), p.9592-9596
Main Authors: Martinho, Marlène, Banse, Frédéric, Bartoli, Jean-François, Mattioli, Tony A, Battioni, Pierrette, Horner, Olivier, Bourcier, Sophie, Girerd, Jean-Jacques
Format: Article
Language:English
Subjects:
Chemical Sciences
Ethylamines - chemistry
Inorganic chemistry
Iron - chemistry
Ligands
Models, Molecular
Molecular Structure
Organometallic Compounds - chemical synthesis
Organometallic Compounds - chemistry
Oxidation-Reduction
Oxygen - chemistry
Pyridines
Pyrimidines - chemistry
Sensitivity and Specificity
Solutions - chemistry
Spectrometry, Mass, Electrospray Ionization - methods
Spectroscopy, Fourier Transform Infrared - methods
Vibration
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Summary:The green complex S = 1 [(TPEN)FeO]2+ [TPEN = N,N,N‘,N‘-tetrakis(2-pyridylmethyl)ethane-1,2-diamine] has been obtained by treating the [(TPEN)Fe]2+ precursor with meta-chloroperoxybenzoic acid (m-CPBA). This high-valent complex belongs to the emerging family of synthetic models of FeIVO intermediates invoked during the catalytic cycle of biological systems. This complex exhibits spectroscopic characteristics that are similar to those of other models reported recently with a similar amine/pyridine environment. Thanks to its relative stability, vibrational data in solution have been obtained by Fourier transform infrared. A comparison of the FeO and Fe18O wavenumbers reveals that the Fe−oxo vibration is not a pure one. The ability of the green complex to oxidize small organic molecules has been studied. Mixtures of oxygenated products derived from two- or four-electron oxidations are obtained. The reactivity of this [FeO]2+ complex is then not straightforward, and different mechanisms may be involved.
ISSN:0020-1669
1520-510X
DOI:10.1021/ic051213y