Abstract
By treating gaseous, liquid, or solid fluorides with UV-photolyzed O(2)/F(2) mixtures and by treating solid oxides with UV-photolyzed F(2) (or O(2)/F(2) mixtures) in liquid anhydrous HF at ambient temperature, we investigated the possibility of the preparation of O(2)M(III)F(4) (M = B, Fe, Co, Ag), O(2)M(IV)F(5) (M = Ti, Sn, Pb), (O(2))(2)M(IV)F(6) (M = Ti, Ge, Sn, Pb, Pd, Ni, Mn), O(2)M(IV)(2)F(9) (M = Sn), O(2)M(V)F(6) (M = As, Sb, Au, Pt), O(2)M(V)(2)F(11) (M = Pt), O(2)M(VI)F(7) (M = Se), (O(2))(2)M(VI)F(8) (M = Mo, W), and O(2)M(VII)F(8) (M = I). The approach has been successful in the case of previously known O(2)BF(4), O(2)MF(6) (M = As, Sb, Au; Pt), O(2)GeF(5), and (O(2))(2)(Ti(7)F(30)). Novel compounds O(2)GeF(5)·HF, α-O(2)Sn(2)F(9) (1-D), and the HF-solvated and nonsolvated forms of β-O(2)Sn(2)F(9) (2-D) were synthesized and their crystal structures determined using single-crystal X-ray diffraction. The crystal structures of all of these materials arise from the condensation of octahedral MF(6) (M = Ge, Sn) units. The anion in the crystal structure of O(2)GeF(5)·HF is comprised of infinite ([GeF(5)](-))(∞) chains of GeF(6) octahedra that share common vertices. The HF molecules and O(2)(+) cations are located between the chains. The crystal structure of α-O(2)SnF(9) (1-D) is constructed from [O(2)](+) cations and polymeric ([Sn(2)F(9)](-))(∞) anions which appear as two parallel infinite chains comprised of SnF(6) units, where each SnF(6) unit of one chain is connected to a SnF(6) unit of the second chain through a shared fluorine vertex. The single-crystal structure determination of [O(2)][Sn(2)F(9)]·0.9HF reveals that it is comprised of two-dimensional ([Sn(2)F(9)](-))(∞) grids with [O(2)](+) cations and HF molecules located between them. The 2-D grids have a wavelike conformation. The ([Sn(2)F(9)](-))(∞) layer contains both six- and seven-coordinated Sn(IV) atoms that are interconnected by bridging fluorine atoms. A new, more complex [O(2)](+) salt, O(2)[Hg(HF)](4)[SbF(6)](9), was prepared. In its crystal structure, the Hg atoms bridge to SbF(6) units to form a 3-D framework. The O(2)(+) cations are located inside the voids while the HF molecules are bound to Hg atoms through the F atom. Attempts to prepare several chlorine analogues of O(2)(+) fluorine salts (i.e., O(2)TiCl(5) and O(2)MCl(6) (M = Nb, Sb)) failed.