The interaction of Lewis acid VOF3 with different fluoride donors in anhydrous hydrogen fluoride solvent is being investigated. This approach resulted in the syntheses and structural characterizations of a variety of new compounds with fluoridomonooxidovanadium(V) anions.The basic building units of this type of anions are [VOF5] octahedra which can associate through fluorine bridges to form more complex oligomeric and polymeric anionic species. The type of anion formed is influenced by the ratio between VOF3? and fluoride anion and the nature of cation.Three different type of anions correspond to the simple (VOF4)- formulation. The most frequently observed species in these systems is an edge-sharing dimer [V2O2F8]2-. The compound with cyclic trimeric anion, [V3O3F12]3-, has also been isolated. A weakly coordinating nature of aforementioned anions is reflected in the formation of coordination compounds with HF or XeF2 ligands.If VOF3 accepts more than one fluoride anion, corner-sharing dimer [V2O2F9]3- or the simple [VOF5]2- anion is formed.Polymeric anions are less frequently observed in the structures of vanadium(V) oxyfluorides. Interestingly, solid-state conformational isomerism exist between [VOF4]nn- corner-sharing chain anions that were found in different compounds. Another type of chain, [V2O2F7]nn-, is formed by alternate corner and edge-sharing between octahedral units.A reaction with XeF2 leads to the formation of XeF2�VOF3 with chain structure and layered XeF2�4VOF3 � a rare examples of XeF2 interacting with metal trifluoride oxide.

Structural diversity of anions formed from vanadium trifluoride oxide in anhydrous hydrogen fluoride

248th National Meeting (2014)

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