Journal article
Reversible (de)protonation-induced valence inversion in mixed-valent diiron(II,III) complexes.
Eric Gouré, Grégory Thiabaud, Michaël Carboni, Nathalie Gon, Patrick Dubourdeaux, Ricardo Garcia-Serres, Martin Clémancey, Jean-Louis Oddou, Adeline Y Robin, Lilian Jacquamet, Lionel Dubois, Geneviève Blondin, Jean-Marc Latour
Inorganic Chemistry | Published : 2011
DOI: 10.1021/ic2007414
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.