Infrared Spectra of the SO₂F₂^– Anion in Solid Argon and Neon

Abstract

Sulfonyl fluoride anion (SOF) was produced during codeposition of laser-ablated metal atoms, ions, and electrons with SOF in argon and neon matrixes at 4 K. The structure of SOF was determined by infrared spectroscopy and density functional theory calculations. On the basis of the experiments using SOF and SOF samples, the three absorptions at 1284.9, 1109.3, and 567.0 cm in argon and 1289.0, 1116.2, and 576.8 cm in neon were assigned to the antisymmetric and symmetric O-S-O stretching and SO wagging modes of SOF, respectively. These assignments were further supported by frequency and isotopic frequency ratio calculations. The SOF anion possesses a A ground state with nonplanar C symmetry. Compared with the neutral SOF molecule, dramatic increases in the S-F bond length (0.295 Å) and F-S-F bond angle (41.0°) were found for the anion, which result from the S-F antibonding character of the singly occupied molecular orbital. The SOF anion was formed via electron capture by SOF in the gas phase before being deposited into the cryogenic matrix. The matrix environment stabilized this anion, but it was destroyed by UV-vis irradiation and presumably converted to the neutral SOF molecule.

Bidentate SO2 Complexes of Zirconium and Hafnium Difluorides with Highly Activated S–O Bonds

“…Metal independent absorptions due to SO 2 and SO 2 F 2 – were observed in all of the experiments, and their intensity are strongly correlated with the laser energy employed. The SO 2 F 2 – bands decreased during sample annealing and almost disappeared upon λ > 220 nm irradiation as reported previously Figure shows the infrared spectra from the reactions of laser ablated Zr atoms and 0.5% SO 2 F 2 in solid argon.…”

“…The SO 2 F 2 − bands decreased during sample annealing and almost disappeared upon λ > 220 nm irradiation as reported previously. 40 The zirconium and hafnium experiments were repeated under the same conditions using both S 18 O 2 F 2 and 34 SO 2 F 2 samples to help the product assignments. The isotopic frequency shifts and ratios obtained from the experiments are diagnostic on the identification of the product structures.…”

Side-On OMoF2(η2-SO) and OWF2(η2-SO) Complexes Featuring Peroxo-Like Sulfur Monoxide Ligand

“…The reactions of molybdenum and tungsten atoms with SO 2 F 2 were studied using different laser energies and various SO 2 F 2 concentrations. Besides the intense SO 2 F 2 precursor absorptions, common absorptions produced after codeposition of laser-ablated metal atoms and SO 2 F 2 such as SO 2 and SO 2 F 2 – were observed in all of the experiments. Figure shows the infrared spectra from the reactions of molybdenum atoms and 0.25% SO 2 F 2 in excess argon.…”

Sulfur Dioxide Complexes of Main-Group Elements: from SO20 to SO2– and SO22– upon Coordination to Aluminum and Silicon Difluorides

“…The infrared spectra showing the reactions of aluminum atoms with 0.5% SO 2 F 2 in neon are given in Figure . In addition to the intense precursor SO 2 F 2 bands, minor absorptions that are common in the reactions of laser-ablated metal atoms and SO 2 F 2 , namely SO 2 F 2 – , SOF 2 , and SO 2 , were observed. Four new aluminum product bands were observed at 971.8, 940.4, 795.6, and 674.8 cm –1 after deposition (Figure , trace a).…”