Raman spectra and structural features of ClOF2 + cation in a solution of anhydrous HF

Abstract

The Raman spectra of CIOF! § cation in solutions of anhydrous HF were studied. In the CIOF2+HF2 -and CIOF2+BF4---HF systems, this cation exists as a pyramidal structure (C s symmetry.), while in the C1OF2+AuF6---HF system, it exists as a planar structure (C2v symmetry). Based on nonempirical calculations by the Hartree--Fock--Roothaan method, an explanation for the dependence of the structure of the C1OF2 + cation on the nature of the anion was proposed. For the C1--O bond vibrations, the correlation functions of vibrational and rotational relaxations were calculated, and the characteristic times of these processes were determined. The main contribution to the formation of the band contours corresponding to the above-mentioned modes is made by the vibrational dephasing.

Photochemistry with Chlorine Trifluoride: Syntheses and Characterization of Difluorooxychloronium(V) Hexafluorido(non)metallates(V), [ClOF2][MF6] (M=V, Nb, Ta, Ru, Os, Ir, P, Sb)

“…Compounds containing the [ClOF 2 ] + cation and a range of different anions, including “[F(HF) n ] − ”, [BF 4 ] − , [MoOF 5 ] − , [Mo 2 O 2 F 9 ] − , [ M F 6 ] − ( M =V, Nb, Ta, U, Pt, Au, P, As, Sb, Bi) and [SiF 6 ] 2− , were previously extensively studied by Raman spectroscopy in hydrogen fluoride solutions and/or in the solid‐state [3, 20, 21, 33–38, 69–71] . In the previous studies, the band assignments were usually based on a C s symmetry for the [ClOF 2 ] + cation either in solution or in the solid‐state.…”

“…Generally, six bands are observed and attributed to the [ClOF 2 ] + cation in most Raman spectra: v (ClO) at ≈1330 cm −1 (usually two separate bands due to the 35 Cl and 37 Cl isotopes), v s (ClF 2 ) at ≈740 cm −1 , v as (ClF 2 ) at ≈710 cm −1 , δ umbrella ([ClOF 2 ]) at ≈510 cm −1 , δ sciss (ClO) at ≈400 cm −1 and δ sciss (ClF 2 ) at ≈380 cm −1 [3, 35] . The frequencies that are assigned to these bands are similar among the [ClOF 2 ][ M F 6 ] compounds, indicating that the [ M F 6 ] − anion has a minor effect.…”

“…, Nb, Ta ,U ,P t, Au, P, As, Sb, Bi)a nd [SiF 6 ] 2À ,w ere previouslye xtensively studied by Raman spectroscopyi nh ydrogenf luoride solutions and/ori nt he solidstate. [3,20,21,[33][34][35][36][37][38][69][70][71] In the previouss tudies, the band assignments were usually based on a C s symmetry for the [ClOF 2 ] + cation either in solution or in the solid-state.…”

“…Compounds with the trigonal pyramidal difluoroxychloronium(V) cation, [ClOF 2 ] + , are obtained in reactions with Lewis acids, such as the pentafluorides M F 5 (Equation ) [20–22, 33–35] …”

“…Compoundsw ith the trigonal pyramidal difluoroxychloronium(V) cation, [ClOF 2 ] + ,a re obtained in reactions with Lewis acids, such as the pentafluorides MF 5 (Equation 3). [20][21][22][33][34][35] ClOF 3 þ MF 5 ! ClOF 2 MF 6 ½ ð3Þ…”