A Charge-Transfer Salt Based on Ferrocene/Ferrocenium Pairs and Keggin-Type Polyoxometalates

A new hybrid inorganic-organometallic salt has been obtained from the reaction of the Keggin-type silicotungstate anion with ferrocene in a water/methanol mixture as a result of the partial oxidation of ferrocene molecules to ferrocenium cations. Single-crystal X-ray diffraction analysis reveals the presence of four ferrocenium (Fe^III) cations and one ferrocene (Fe^II) molecule per plenary Keggin anion in the crystal structure of [Fe^III (Cp)₂]₄[SiW₁₂O₄₀]·[Fe^II(Cp)₂]·2CH₃OH (1). Compound 1 thus constitutes the first example in the literature in which ferrocenium and ferrocene species coexist in the structure of a polyoxometalate-based salt. The two crystallographically independent ferrocenium species in the asymmetric unit of 1 exhibit different configurations: One displays an eclipsed conformation with ideal D symmetry, whereas the conformation in the other one is staggered D. The crystal packing of 1 can be best described as an organometallic sub-lattice of ferrocenium and ferrocene species linked by a network of π-π interactions that generates rectangular cavities of about 14 × 10 Å in which strings of Keggin anions and methanol molecules are hosted, further connected to each other via weak O_POM···C_MeOH-O_MeOH···O_POM type hydrogen bonds. The charge-transfer nature of the salt has been studied by solid-state diffuse reflectance UV-Vis spectroscopy and the presence of magnetically isolated Fe^III/Fe^II centres has been confirmed by Mössbauer spectroscopy. A topological study carried out on all of the pristine ferrocenyl species deposited in the Cambridge Structural Database (CSD) has allowed two main conclusions to be drawn: (1) these species tend to adopt extreme conformations (either eclipsed or staggered) with less than a 15% of examples showing intermediate states and (2) the oxidation state of the iron centres can be unequivocally assigned on the basis of a close inspection of the Fe···Cp distances, which allows ferrocene neutral molecules and ferrocenium cations to be easily distinguished.