Journal ArticleDOI
FeIII‐Hydroperoxo and Peroxo Complexes with Aminopyridyl Ligands and the Resonance Raman Spectroscopic Identification of the Fe−O and O−O Stretching Modes
A. Jalila Simaan,Susanne Döpner,Frédéric Banse,Sophie Bourcier,Guy Bouchoux,Alain Boussac,Peter Hildebrandt,Jean-Jacques Girerd +7 more
TLDR
In this paper, the spectral properties of nonheme Fe(III)-peroxo complexes with aminopyridyl-type ligands have been characterized by UV/Vis, EPR, mass and Resonance Raman spectroscopy.Abstract:
Nonheme Fe(III)-hydroperoxo and Fe(III)-peroxo complexes with aminopyridyl-type ligands have been prepared and characterized by UV/Vis, EPR, mass and Resonance Raman (RR) spectroscopy. The Fe(III)(OOH) species are low-spin and exhibit a deep purple color due to the ligand-to-metal charge transfer (LMCT) hand centered at ca. 550 nm. The RR spectra of the Fe(III)(OOH) complexes display two bands at ca. 620 and 800 cm-1 that are assigned to the respective Fe-O and O-O stretching modes on the basis of the characteristic H/D and 16O/18O frequency shifts. Upon deprotonation, Fe(III)(O2) species are obtained which possess a high-spin configuration of nearly axial symmetry and a LMCT transition in the near infrared (ca. 750 nm). The frequencies of the Fe-O and O-O stretching modes at ca. 465 and 820 cm-1, as well as their respective 16O/18O shifts of -16 and -45 cm-1, indicate an ?2 coordination geometry for the Fe(III)(O2) complex.read more
Citations
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Dioxygen activation at mononuclear nonheme iron active sites: enzymes, models, and intermediates.
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Mononuclear non-heme iron enzymes with the 2-His-1-carboxylate facial triad: recent developments in enzymology and modeling studies.
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Synthetic analogues of cysteinate-ligated non-heme iron and non-corrinoid cobalt enzymes
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Asymmetric epoxidation with H2O2 by manipulating the electronic properties of non-heme iron catalysts.
TL;DR: Electronic effects imposed by the ligand on the iron center are shown to synergistically cooperate with catalytic amounts of carboxylic acids in promoting efficient O-O cleavage and creating highly chemo- and enantioselective epoxidizing species which provide a broad range of epoxides in synthetically valuable yields and short reaction times.
References
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Book
The Theory of Transition-Metal Ions
TL;DR: In this paper, the strong-filed coupling scheme was proposed to overcome the weak-field coupling scheme in paramagnetic resonance, which was shown to be effective in the case of free atoms and ions.
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Heme-Containing Oxygenases
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Stereospecific Alkane Hydroxylation with H2O2 Catalyzed by an Iron(II)−Tris(2-pyridylmethyl)amine Complex
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The EPR of low spin heme complexes. Relation of the t2g hole model to the directional properties of the g tensor, and a new method for calculating the ligand field parameters.
TL;DR: A simple method is presented for calculating the parameters of the hole model for distorted octahedral, low spin (t2g)5 complexes, with explicit formulas for the coefficients of the Kramer's doublet, where g defines the plane and orientation of the orbital with the largest coefficient, which indicates the directions of maximal unpaired spin density.