RESUMEN
Robust mono-, di-, and tridentate base-stabilized thionylium (SO2+) dications were synthesized from the treatment of SOCl2 with Me3SiO3SCF3 and pyridine-based ligands. Computational and experimental data are consistent with Lewis acidities comparable to BF3 and PF5 and these compounds were shown to activate C-F bonds of fluoroalkanes. These dications also react with Ph3PO and CuO to effect O2- abstraction in an overall redox-neutral deoxygenation process driven by the evolution of SO2.
RESUMEN
The reaction of Hg(AsF6 )2 with a large molar excess of KrF2 in anhydrous HF has afforded the first homoleptic KrF2 coordination complex of a metal cation, [Hg(KrF2 )8 ][AsF6 ]2 â 2 HF. The [Hg(KrF2 )8 ]2+ dication is well-isolated in the low-temperature crystal structure of its HF-solvated [AsF6 ]- salt, and consists of eight KrF2 molecules that are terminally coordinated to Hg2+ by means of Hg-F(KrF) bonds to form a slightly distorted, square-antiprismatic coordination sphere around mercury. The Raman spectrum of [Hg(KrF2 )8 ]2+ was assigned with the aid of calculated gas-phase vibrational frequencies. Computational studies indicate that both electrostatic and orbital interactions are important for metal-ligand bonding and provide insight into the geometry of the [Hg(KrF2 )8 ]2+ cation and the nature of noble-gas difluoride ligand bonding.
RESUMEN
Acetonitrile and [FXeOXe- - -FXeF][AsF6 ] react at -60 °C in anhydrous HF (aHF) to form the CH3 CN adduct of the previously unknown [XeOXe](2+) cation. The low-temperature X-ray structure of [CH3 CN- - -XeOXe- - -NCCH3 ][AsF6 ]2 exhibits a well-isolated adduct-cation that has among the shortest Xe-N distances obtained for an sp-hybridized nitrogen base adducted to xenon. The Raman spectrum was fully assigned by comparison with the calculated vibrational frequencies and with the aid of (18) O-enrichment studies. Natural bond orbital (NBO), atoms in molecules (AIM), electron localization function (ELF), and molecular electrostatic potential surface (MEPS) analyses show that the Xe-O bonds are semi-ionic whereas the Xe-N bonds may be described as strong electrostatic (σ-hole) interactions.
