NDLI: Reactivity of Molecular Dioxygen towards a Series of Isostructural Dichloroiron(III) Complexes with Tripodal Tetraamine Ligands: General Access to μ-Oxodiiron(III) Complexes and Effect of α-Fluorination on the Reaction Kinetics

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Reactivity of Molecular Dioxygen towards a Series of Isostructural Dichloroiron(III) Complexes with Tripodal Tetraamine Ligands: General Access to μ-Oxodiiron(III) Complexes and Effect of α-Fluorination on the Reaction Kinetics

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Reactivity of Molecular Dioxygen towards a Series of Isostructural Dichloroiron(III) Complexes with Tripodal Tetraamine Ligands: General Access to μ-Oxodiiron(III) Complexes and Effect of α-Fluorination on the Reaction Kinetics

Content Provider	World Health Organization (WHO)-Global Index Medicus
Author	Humbert, Nicolas Thallaj, Nasser K. Rotthaus, Olaf Benhamou, Leila Elhabiri, Mourad Albrecht-gary, Anne-marie Welter, Richard Mandon, Dominique Lachkar, Mohammed
Description	Author Affiliation: Thallaj NK ( Laboratoire de Chimie Biomimétique des Métaux de Transition, Institut de Chimie, UMR CNRS 7177-LC 3, Université Louis Pasteur, 4 rue Blaise Pascal, Strasbourg cedex, France.)
Abstract	We have synthesized the mono, di-, and tri-α-fluoro ligands in the tris(2-pyridylmethyl)amine (TPA) series, namely, FTPA, $F_{2}TPA$ and $F_{3}TPA,$ respectively. Fluorination at the α-position of these nitrogen-containing tripods shifts the oxidation potential of the ligand by 45–70 mV per added fluorine atom. The crystal structures of the dichloroiron(II) complexes with FTPA and $F_{2}TPA$ reveal that the iron center lies in a distorted octahedral geometry comparable to that already found in $TPAFeCl_{2}.$ All spectroscopic data indicate that the geometry is retained in solution. These three isostructural complexes all react with molecular dioxygen to yield stable μ-oxodiiron(III) complexes. Crystal structure analyses are reported for each of these three μ-oxo compounds. With TPA, a symmetrical structure is obtained for a dicationic compound with the tripod coordinated in the $κ^{4}N$ coordination mode. With FTPA, the compound is a neutral μ-oxodiiron(III) complex with a $κ^{3}N$ coordination mode of the ligand. Oxygenation of the $F_{2}TPA$ complex gave a neutral unsymmetrical compound, the structure of which is reminiscent of that already found with the trifluorinated ligand. On reduction, all μ-oxodiiron(III) complexes revert to the starting iron(II) species. The oxygenation reaction parallels the well-known formation of μ-oxo derivatives from dioxygen in the chemistry of porphyrins reported almost three decades ago. The striking feature of the series of iron(II) precursors is the effect of the ligand on the kinetics of oxygenation of the complexes. Whereas the parent complex undergoes 90 % conversion over 40 h, the monofluorinated ligand provides a complex that has fully reacted after 30 h, whereas the reaction time for the complex with the difluorinated ligand is only 10 h. Analysis of the spectroscopic data reveals that formation of the μ-oxo complexes proceeds in two distinct reversible kinetic steps with $k_{1}≈10 k_{2}.$ For $TPAFeCl_{2}$ and $FTPAFeCl_{2}$ only small variations in the $k_{1}$ and $k_{2}$ values are observed. By contrast, $F_{2}TPAFeCl_{2}$ exhibits $k_{1}$ and $k_{2}$ values that are ten times higher. These differences in kinetics are interpreted in the light of structural and electronic effects, especially the Lewis acidity at the metal center. Our results suggest coordination of dioxygen as an initial step in the process leading to formation of μ-oxodiiron(III) compounds, by contrast with an unlikely outer-sphere reduction of dioxygen, which generally occurs at negative potentials.
ISSN	09476539
e-ISSN	15213765
Journal	Chemistry - A European Journal
Issue Number	22
Volume Number	14
Language	English
Publisher	Wiley-VCH;ChemPubSoc Europe
Publisher Date	2008-01-01
Publisher Place	Germany
Access Restriction	Open
Subject Keyword	Amines Chemistry Ferric Compounds Fluorine Oxygen Electrochemistry Kinetics Ligands Magnetic Resonance Spectroscopy Models, Molecular X-Ray Diffraction Research Support, Non-U.S. Gov't
Content Type	Text
Resource Type	Article
Subject	Organic Chemistry Catalysis

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