Fe(II) and Fe(III) Mononuclear Complexes with a Pentadentate Ligand Built on the 1,3-Diaminopropane Unit. Structures and Spectroscopic and Electrochemical Properties. Reaction with H2O2
- 12 March 2003
- journal article
- research article
- Published by American Chemical Society (ACS) in Inorganic Chemistry
- Vol. 42 (7) , 2470-2477
- https://doi.org/10.1021/ic025905n
Abstract
Two new iron complexes, [L(5)(3)Fe(II)Cl]PF(6) (1.PF(6)) and [(L(5)(3)H(+))Fe(III)Cl(3)]PF(6) (2.PF(6)), were synthesized (L(5)(3) = N-methyl-N,N',N'-tris(2-pyridylmethyl)propane-1,3-diamine), and their molecular structures were determined by X-ray crystallography. Their behavior in solution was studied by UV-vis spectroscopy and electrochemistry. Upon addition of a base to an acetonitrile solution of 2, the new unsymmetrical dinuclear complex [L(5)(3)Fe(III)OFe(III)Cl(3)](+) was detected. Treating 1 with hydrogen peroxide has allowed us to detect the low spin [L(5)(3)Fe(III)OOH](2+). Its spectroscopic properties (UV-vis, EPR and resonance Raman) are similar to those reported for related FeOOH complexes obtained with amine/pyridine ligands. Using stopped-flow absorption spectroscopy, the formation and degradation of [L(5)(3)Fe(III)OOH](2+) has been monitored, and a mechanism is proposed to reproduce the kinetic data.Keywords
This publication has 24 references indexed in Scilit:
- Sulfide Oxidation by Hydrogen Peroxide Catalyzed by Iron Complexes: Two Metal Centers Are Better Than OneChemistry – A European Journal, 2002
- The Electronic Structure of Non-Heme Iron(III)−Hydroperoxo and Iron(III)−Peroxo Model Complexes Studied by Mössbauer and Electron Paramagnetic Resonance SpectroscopiesInorganic Chemistry, 2001
- Iron Chemistry of a Pentadentate Ligand That Generates a Metastable FeIII−OOH IntermediateInorganic Chemistry, 1999
- Complexes with FeIII2(μ-O)(μ-OH), FeIII2(μ-O)2, and [FeIII3(μ2-O)3] Cores: Structures, Spectroscopy, and Core InterconversionsJournal of the American Chemical Society, 1999
- Electrochemical properties of [FeIII(L)2Cl2][PF6] and [Fe2III,IIIO(L)4Cl2][PF6]2 [L=2,2′-bipyridine (bpy) and 4,4′-dimethyl-2,2′-bipyridine (dmbpy)]. Crystal structures of the dmbpy derivativesNew Journal of Chemistry, 1999
- EPR Spectroscopic Reinvestigation of the Activation of Iron Complexes of PMAH as a Bleomycin ModelJournal of the American Chemical Society, 1998
- Reduced Oxy Intermediate Observed in D251N Cytochrome P450camBiochemistry, 1997
- Structure and Electrochemical Studies of [(trispicMeen)ClFeIIIOFeIIICl(trispicMeen)]2+. Spectroscopic Characterization of the Mixed-Valence FeIIIOFeII Form. Relevance to the Active Site of Dinuclear Iron−Oxo ProteinsInorganic Chemistry, 1997
- Heme-Containing OxygenasesChemical Reviews, 1996
- Dissymmetry effects in .mu.-oxo diiron(III) species: structures and spectroscopic properties of [N5FeOFeX3]+ (X = Cl, Br) and implications for oxo-bridged dinuclear iron proteinsJournal of the American Chemical Society, 1989