X-ray crystal structures of [XeF][MF6] (M = As, Sb, Bi), [XeF][M2F11] (M = Sb, Bi) and estimated thermochemical data and predicted stabilities for noble-gas fluorocation salts using volume-based thermodynamics.

The crystal structures of the xenon(II) salts, [XeF][SbF(6)], [XeF][BiF(6)], and [XeF][Bi(2)F(11)], have been determined for the first time, and those of XeF(2), [XeF][AsF(6)], [XeF][Sb(2)F(11)], and [XeF(3)][Sb(2)F(11)] have been redetermined with greater precision at -173 °C. The Bi(2)F(11)(-) anion, which has a structure analogous to those of the As(2)F(11)(-) and Sb(2)F(11)(-) anions, has been structurally characterized by single crystal X-ray diffraction for the first time as its XeF(+) salt. The fluorine bridge between the bismuth atoms is asymmetric with Bi---F(b) bond lengths of 2.

Behavior of BrO3F and ClO3F toward strong Lewis acids and the characterization of [XO2][SbF6] (X = Cl, Br) by single crystal X-ray diffraction, Raman spectroscopy, and computational methods.

The interactions of BrO3F and ClO3F with the strong Lewis acids AsF5 and SbF5 were investigated. Although ClO3F is unreactive toward AsF5 and SbF5, BrO3F undergoes fluoride ion abstraction and O2 elimination, accompanied by central halogen reduction, to form [BrO2][Sb(n)F(5n+1)] (n > or = 1), rather than simple fluoride ion abstraction to form BrO3(+) salts. The geometric parameters of the BrO2(+) cation have been obtained in the solid state for the first time by a single-crystal X-ray diffraction study of [BrO2][SbF6] at -173 degrees C and are compared with those of ClO2(+) salts.

Synthesis and characterization of salts containing the BrO(3)F(2)(-) anion; a rare example of a bromine(VII) species.

The BrO(3)F(2)(-) anion has been prepared by reaction of BrO(3)F with the fluoride ion donors KF, RbF, CsF, [N(CH(3))(4)][F], and NOF. The BrO(3)F(2)(-) anion is only the fourth Br(VII) species to have been isolated in macroscopic quantities, and it is one of only three oxide fluorides that possess D(3)(h)() symmetry, the others being XeO(3)F(2) and OsO(3)F(2). The fluoride ion acceptor properties of BrO(3)F contrast with those of ClO(3)F, which does not react with the strong fluoride ion donor [N(CH(3))(4)][F] to form the analogous ClO(3)F(2)(-) salt.

X-ray crystal structures of [XF(6)][Sb(2)F(11)] (X = Cl, Br, I); (35,37)Cl, (79,81)Br, and (127)I NMR studies and electronic structure calculations of the XF(6)(+) cations.

The single-crystal X-ray structures of [XF(6)][Sb(2)F(11)] (X = Cl, Br, I) have been determined and represent the first detailed crystallographic study of salts containing the XF(6)(+) cations. The three salts are isomorphous and crystallize in the monoclinic space group P2(1)/n with Z = 4: [ClF(6)][Sb(2)F(11)], a = 11.824(2) A, b = 8.