Xenon anions

Table 2. Fluoro- and Oxofluoro-Cations and Anions of Xenon, Their Parent Compounds, and Geometries...

Xenon Bonded to Carbon. A number of stmcturally well-characterized compounds containing Xe—C bonds are known. In all cases these occur as colorless salts of xenonium cations, R—Xe" where R is a fluorophenyl or alkynyl group. The formation of the pentafluorophenylxenon(II) cation, CgFgXe+ [121850-39-3] (-30W) and CHgC N (0°C) solutions with the anions B(C3F3)3F [121850-40-6], B(CgFg) 2F- [123168-25-2], and... 

The starting point for the synthesis of xenon compounds is the preparation of xenon difluoride, XeF2, and xenon tetrafluoride, XeF4, by heating a mixture of the elements to 400°C at 6 atm. At higher pressures, fluorination proceeds as far as xenon hexafluoride, XeFfi. All three fluorides are crystalline solids (Fig. 15.27). In the gas phase, all are molecular compounds. Solid xenon hexafluoride, however, is ionic, with a complex structure consisting of XeF< + cations bridged by F anions. 

A cation containing two xenon atoms, Xe2Fu+, is also known, and it has a structure that can be shown as F5Xe+"-F -" XeF5+. Polyatomic anions containing xenon are produced because XeFs is also a Lewis acid. An example of this type of reaction can be shown as... 

Comment on heats of formation of fluoro-anions, and electron and fluoride-ion affinities of neutral fluorides, measured mass spectropho-tometrically (57,185,216,222) or derived from salt values obained by conventional calorimetry (32, 45, 46, 105) needs to be reserved until better agreement is reached between methods. However, from measurements on heats of formation of the predominantly ionic xenon fluoride adducts it has been possible to show the trend to increasing ionic-ity with pentafluoride partners Nb < Ta < Sb, which parallels the increasing Lewis acidity of these fluorides found by independent methods (44). 

Germanes hydride, 2 76 reactivity of, 2 87 Germanium anionic cluster, 24 227 azides, preparation, 9 138 properties, 9 135-136, 139, 141 binary carbide not reported, 11 211 carbides, preparation of, 11 163 chalcogenide halides, 23 390 chlorides, mass spectra of, 18 248, 249 complexes, xenon fluoride reactions, 46 85 compounds, see also Organogermanium compounds... 

Xenon hexafluoride can act as a Lewis acid. It reacts with the heavier alkali fluorides to form seven-coordinate anions, which in turn can rearrange to form eight-coordinate species ... 

The octalluoroxenaies are the most stable xenon compounds known they can be heated to 400 °C without decomposition. The anions have square antiprismatic geometry. They, too, present a problem to VSEPR theory analogous to that of XeF6 since they should also have a stereochemically active lone pair of electrons that should lower the symmetry of the anion. If the steric crowding theory is correct, however, the presence of eight ligand atom/, could force the lone pair into a stereochemically inert s Orhital. 

Xenon fluorides can also act as fluoride ion donors. Strong Lewis acids react with xenon fluorides to yield the expected compounds, but since both the ealiome and anionic species can form fluoride bridges, the stoichiometries may appear strange at limes ... 

The first metal-xenon compound with direct Au—Xe bonds has been reported by Seidel and Seppelt1027-1029 [Eq. (4.252)]. The salt crystallizes in two crystallographic modifications differing in cation-anion interactions. In each form the cation is a regular square. In the triclinic modification the Au—Xe bond lengths are between 2.7330 A and 2.7779 A and there are three weak interionic contacts (Au—F... 

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