Preparation, structures and properties of oxalate-bridged binuclear iron(III) complex: [(acac)2Fe(μ-ox)Fe(acac)2] and [(acac)2Fe(μ-ox)Fe(acac)2]·CH2ClCH2Cl

An oxalate-bridged binuclear iron(III) complex, [(acac)2Fe(μ-ox)Fe(acac)2], (acac−=acetylacetonate anion and ox2−=oxalate anion) was prepared. The complex crystallized as two types of crystals under different conditions: one had 1,2-dichloroethane as a solvent molecule of crystallization 2, the other did not 1. Both compounds have been characterized by X-ray crystallography, infrared spectroscopy, and thermogravimetric analysis. Compound 1 has also been characterized by UV–Vis and 1H NMR spectroscopies, mass spectrometry, and electrochemistry. In both crystals, each iron(III) is coordinated in an octahedral arrangement by the oxygen atoms of an oxalate-bridging ligand and four oxygen atoms belonging to peripheral acac ligands in an octahedral arrangement. The intermetallic distance of Fe⋯Fe is 5.4368(9) Å in 1 and 5.438(2) Å in 2. Two iron(III) ions in each crystal are bridged by the oxalate and both lie in the oxalate-plane. The results of thermal analyses imply that the thermal stability of 2 is lower than that of 1. Cyclic voltammograms of 1 in acetonitrile and dichloromethane at low temperature showed two consecutive, quasi-Nernstian, one-electron reduction steps corresponding to the reduction of FeIII–FeIII to FeIII–FeII followed by the reduction of FeIII–FeII to FeII–FeII. The electrochemical comproportionation constants (Kc) of the equilibrium (FeIII–FeIII) + (FeII–FeII) ⇌ 2(FeIII–FeII) are 108.9 in acetonitrile medium and 108.5 in dichloromethane, respectively. The considerably large Kc values indicate that the main factor contributing to the stabilization of the FeIII–FeII mixed-valence state is electronic delocalization through the oxalate-bridge.