Photochemistry with ClF₃ – An Access to [ClOF₂]⁺ Salts

Abstract

A route to salts of the [ClOF2]+ cation is described that does not require the parent fluoride ClOF3 as a starting material. These can be obtained when either metals such as Cr, Rh, Pd and Au, halides such as PtCl2, SnF2 and PbF4, or oxides such as B2O3, OsO4, GeO2, SnO and Sb2O4 are reacted with ClF3 and additional O2, where necessary, under UV irradiation. Cr, Rh, Pd, PtCl2, GeO2, and SnO formed salts with the respective hexafluoridometallate(IV) anion with the composition [ClOF2]2[MF6]. They crystallize in two distinct structure types in either the monoclinic crystal system (M=Cr, Rh, Ge) or the orthorhombic one (M=Pd, Pt, Sn). The fluorides SnF2 and PbF4 were converted to the monoclinic salts [ClOF2]MF5, and B2O3 formed orthorhombic [ClOF2][BF4]. The triclinic compound ([ClOF2][OsO3F3])2⋅OsF6 was obtained from OsO4 and contains a neutral co‐crystallized OsF6 molecule. A monoclinic double salt with the composition [ClOF2]2[AuF4][SbF6] was obtained by reacting a mixture of Sb2O4 and Au. The compounds were investigated by single crystal X‐ray diffraction and IR and Raman spectroscopy. Quantum‐chemical calculations for the solid‐state allowed for the band assignments of the vibrational spectra.

Discrete Mono-, Di-, and Trinuclear Anions [MoOF5]−, [MoVOF5]2–, [MoO2F4]2–, [Mo2O2F9]−, [Mo3O3F13]−, and the Infinite Chain Anion [MoO2F3]− Obtained from Reactions of MoOF4: Synthesis and Analysis of the Structure-Chemical Relations of the Compounds

“…The Cl–O bond length in the [ClOF 2 ] + cation is 1.4630(14) Å and is slightly longer compared to other [ClOF 2 ] + compounds. The Cl–F bond lengths are with 1.4968(14) and 1.5554(12) Å comparable to other [ClOF 2 ] + salts. , …”

“…The respective bond lengths in [BrOF 2 ] + are with 1.564(5) Å for Br–O and 1.727(4) and 1.723(4) Å for Br–F longer compared to the [ClOF 2 ] + cation in [ClOF 2 ]­[Mo 3 O 3 F 13 ] due to the larger ionic radius of bromine. The coordination number of six for the Cl atom is observed in several other [ClOF 2 ] + -containing compounds. , …”

“…) Å for Br−O and 1.727(4) and 1.723(4) Å for Br−F longer compared to the [ClOF 2 ] + cation in [ClOF 2 ]-[Mo 3 O 3 F 13 ] due to the larger ionic radius of bromine. The coordination number of six for the Cl atom is observed in several other [ClOF2] + -containing compounds 47,48. The molybdenum atoms Mo(1), Mo(2), and Mo(3) each occupy the general site 2i and are each surrounded by one oxygen atom and five fluorine atoms in the form of distorted octahedra.…”

“…Comparison of Bond Lengths of MoOF 4 and the Mononuclear Anions Discussed So Far. In Table 3, By the interaction of cations and anions, a two-dimensional infinite layer parallel to the ab plane is formed that can be described with the Niggli formula AgF F F 47,48 Beside the [ClOF 2 ] + cation, the [BrOF 2 ] + cation is also known. 49 The respective bond lengths in [BrOF 2 ] + are with 1.564( 5 16), which can be described with the Niggli formula given in the Supporting Information.…”

Polyanion Condensation in Inorganic and Hybrid Fluoridometallates (IV) of Octahedrally Coordinated Ti, Zr, Hf, V, Cr, W, Mn, Ge, Sn, and Pb

“…The crystal structures of ClOF 2 SnF 5 and ClOF 2 PbF 5 are isotypic ( Table 12 ) [ 36 ]. The polymeric ([SnF 5 ] − ) n anion has a similar chain-like geometry (Sn–F: 1.901(6)–2.061(5) Å and Sn–Fb–Sn = 143.31°) as in ClO 2 SnF 5 .…”