0000000000204527
AUTHOR
Gary J. Schrobilgen
showing 3 related works from this author
Synthesis, vibrational and NMR spectroscopic characterization of [N(CH3)4][IO2F2] and X-ray crystal structure of [N(CH3)4]2[IO2F2][HF2]
2004
Abstract The salt, [N(CH3)4][IO2F2], was prepared from [N(CH3)4][IO3] and 49% aqueous HF, and characterized by Raman, infrared, and 19F NMR spectroscopy. Crystals of [N(CH3)4]2[IO2F2][HF2] were obtained by reduction of [N(CH3)4][cis-IO2F4] in the presence of [N(CH3)4][F] in CH3CN solvent and were characterized by Raman spectroscopy and single-crystal X-ray diffraction: C2/m, a = 14.6765(2) A, b = 8.60490(10) A, c = 13.9572(2) A, β = 120.2040(10)°, V = 1523.35(3) A3, Z = 4 and R = 0.0192 at 210 K. The crystal structure consists of two I O 2 F 2 − anions that are symmetrically bridged by two H F 2 − anions, forming a [F2O2I(FHF)2IO2F2]4− dimer. The symmetric bridging coordination for the H F …
NMR Spectroscopic Evidence for the Intermediacy of XeF3− in XeF2/F− Exchange, Attempted Syntheses and Thermochemistry of XeF3− Salts, and Theoretical…
2010
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…
Energetics of hydride and electron pair attachment to EX30/+ (E=B, C, Al, Si and X=F, Cl, Br, I) and the study of bonding trends among EX30/+, EX32−/…
2004
Abstract A theoretical gas-phase “ligand-free” or “electron pair affinity” (EPA) approach, based on CCSD(T)/(SDB-)cc-pVTZ//MP2/(SDB-)cc-pVTZ electronic structure calculations, is introduced as a possible means for determining Lewis acidity trends among planar EX30/+ (E = B, C, Al, Si; X = F, Cl, Br, I) species. In this treatment, the free electron pair is considered to be an extreme Lewis base. The calculated EPA values are compared with experimental Lewis acidities, previously calculated fluoride ion affinity (FIA) and hydride ion affinity (HA) trends, and are found to exhibit reasonable correlations in all cases. The bonding in the planar and trigonal pyramidal conformations of EX30/+ and…