title: Reversible (de)protonation-induced valence inversion in mixed-valent diiron(II,III) complexes.
abstract: The coupling of electron and proton transfers is currently under intense scrutiny. This Communication reports a new kind of proton-coupled electron transfer within a homodinuclear first-row transition-metal complex. The triply-bridged complex [Fe(III)(μ-OPh)(μ(2)-mpdp)Fe(II)(NH(2)Bn)] (1; mpdp(2-) = m-phenylenedipropionate) bearing a terminal aminobenzyl ligand can be reversibly deprotonated to the anilinate complex 2 whose core [Fe(II)(μ-OPh)(μ(2)-mpdp)Fe(III)(NHBn)] features an inversion of the iron valences. This observation is supported by a combination of UV-visible, (1)H NMR, and Mössbauer spectroscopic studies.
authors.affiliation: Laboratoire de Chimie et Biologie des Métaux-pmb UMR 5249, UJF-Grenoble 1/CEA-DSV-iRTSV/CNRS, Grenoble F-38054, France.
authors.forename: Eric
authors.initials: E
authors.lastname: Gouré
authors.forename: Grégory
authors.initials: G
authors.lastname: Thiabaud
authors.forename: Michaël
authors.initials: M
authors.lastname: Carboni
authors.forename: Nathalie
authors.initials: N
authors.lastname: Gon
authors.forename: Patrick
authors.initials: P
authors.lastname: Dubourdeaux
authors.forename: Ricardo
authors.initials: R
authors.lastname: Garcia-Serres
authors.forename: Martin
authors.initials: M
authors.lastname: Clémancey
authors.forename: Jean-Louis
authors.initials: JL
authors.lastname: Oddou
authors.forename: Adeline Y
authors.initials: AY
authors.lastname: Robin
authors.forename: Lilian
authors.initials: L
authors.lastname: Jacquamet
authors.forename: Lionel
authors.initials: L
authors.lastname: Dubois
authors.forename: Geneviève
authors.initials: G
authors.lastname: Blondin
authors.forename: Jean-Marc
authors.initials: JM
authors.lastname: Latour
mesh_terms: D018360:Crystallography, X-Ray; D004583:Electrons; D005290:Ferric Compounds / Q000737:chemistry*; D005296:Ferrous Compounds / Q000737:chemistry*; D008024:Ligands; D008958:Models, Molecular; D008968:Molecular Conformation; D011522:Protons; D013237:Stereoisomerism
chemical_list: D005290:Ferric Compounds; D005296:Ferrous Compounds; D008024:Ligands; D011522:Protons