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Inorganic Chemistry, Vol.44, No.25, 9592-9596, 2005
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 = NN,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 highvalent complex belongs to the emerging family of synthetic models of Fe-IV=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=O-18 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.