title: NMR spectroscopic evidence for the intermediacy of XeF(3)(-) in XeF(2)/F(-) exchange, attempted syntheses and thermochemistry of XeF(3)(-) salts, and theoretical studies of the XeF(3)(-) anion.
abstract: The existence of the trifluoroxenate(II) anion, XeF(3)(-), had been postulated in a prior NMR study of the exchange between fluoride ion and XeF(2) in CH(3)CN solution. The enthalpy of activation for this exchange, ΔH(⧧), has now been determined by use of single selective inversion (19)F NMR spectroscopy to be 74.1 ± 5.0 kJ mol(-1) (0.18 M) and 56.9 ± 6.7 kJ mol(-1) (0.36 M) for equimolar amounts of [N(CH(3))(4)][F] and XeF(2) in CH(3)CN solvent. Although the XeF(3)(-) anion has been observed in the gas phase, attempts to prepare the Cs(+) and N(CH(3))(4)(+) salts of XeF(3)(-) have been unsuccessful, and are attributed to the low fluoride ion affinity of XeF(2) and fluoride ion solvation in CH(3)CN solution. The XeF(3)(-) anion would represent the first example of an AX(3)E(3) valence shell electron pair repulsion (VSEPR) arrangement of electron lone pair and bond pair domains. Fluorine-19 exchange between XeF(2) and the F(-) anion has also been probed computationally using coupled-cluster singles and doubles (CCSD) and density functional theory (DFT; PBE1PBE) methods. The energy-minimized geometry of the ground state shows that the F(-) anion is only weakly coordinated to XeF(2) (F(2)Xe---F(-); a distorted Y-shape possessing C(s) symmetry), while the XeF(3)(-) anion exists as a first-order transition state in the fluoride ion exchange mechanism, and is planar and Y-shaped (C(2v) symmetry). The molecular geometry and bonding of the XeF(3)(-) anion has been described and rationalized in terms of electron localization function (ELF) calculations, as well as the VSEPR model of molecular geometry. Quantum-chemical calculations, using the CCSD method and a continuum solvent model for CH(3)CN, accurately reproduced the transition-state enthalpy observed by (19)F NMR spectroscopy, and showed a negative but negligible enthalpy for the formation of the F(2)Xe---F(-) adduct in this medium.
authors.affiliation: Department of Chemistry, McMaster University, Hamilton, Ontario L8S 4M1, Canada.
authors.forename: Neil
authors.initials: N
authors.lastname: Vasdev
authors.forename: Matthew D
authors.initials: MD
authors.lastname: Moran
authors.forename: Heikki M
authors.initials: HM
authors.lastname: Tuononen
authors.forename: Raman
authors.initials: R
authors.lastname: Chirakal
authors.forename: Reijo J
authors.initials: RJ
authors.lastname: Suontamo
authors.forename: Alex D
authors.initials: AD
authors.lastname: Bain
authors.forename: Gary J
authors.initials: GJ
authors.lastname: Schrobilgen
mesh_terms: D000097:Acetonitriles / Q000737:chemistry*; D000838:Anions / Q000737:chemistry; D005459:Fluorides / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D011789:Quantum Theory; D012492:Salts / Q000737:chemistry; D013816:Thermodynamics; D014978:Xenon / Q000737:chemistry*
chemical_list: D000097:Acetonitriles; D000838:Anions; D012492:Salts; D014978:Xenon; C048007:xenon fluoride; D005459:Fluorides