Syntheses of Dioxygenyl Salts by Photochemical Reactions in Liquid Anhydrous Hydrogen Fluoride: X-ray Crystal Structures of α- and β-O₂Sn₂F₉, O₂Sn₂F₉·0.9HF, O₂GeF₅·HF, and O₂[Hg(HF)]₄(SbF₆)₉

Abstract

By treating gaseous, liquid, or solid fluorides with UV-photolyzed O2/F2 mixtures and by treating solid oxides with UV-photolyzed F2 (or O2/F2 mixtures) in liquid anhydrous HF at ambient temperature, we investigated the possibility of the preparation of O2MIIIF4 (M = B, Fe, Co, Ag), O2MIVF5 (M = Ti, Sn, Pb), (O2)2MIVF6 (M = Ti, Ge, Sn, Pb, Pd, Ni, Mn), O2MIV 2F9 (M = Sn), O2MVF6 (M = As, Sb, Au, Pt), O2MV 2F11 (M = Pt), O2MVIF7 (M = Se), (O2)2MVIF8 (M = Mo, W), and O2MVIIF8 (M = I). The approach has been successful in the case of previously known O2BF4, O2MF6 (M = As, Sb, Au; Pt), O2GeF5, and (O2)2(Ti7F30). Novel compounds O2GeF5·HF, α-O2Sn2F9 (1-D), and the HF-solvated and nonsolvated forms of β-O2Sn2F9 (2-D) were synthesized and their crystal structures determined using single-crystal X-ray diffraction. The crystal structures of all of these materials arise from the condensation of octahedral MF6 (M = Ge, Sn) units. The anion in the crystal structure of O2GeF5·HF is comprised of infinite ([GeF5]−)∞ chains of GeF6 octahedra that share common vertices. The HF molecules and O2 + cations are located between the chains. The crystal structure of α-O2SnF9 (1-D) is constructed from [O2]+ cations and polymeric ([Sn2F9]−)∞ anions which appear as two parallel infinite chains comprised of SnF6 units, where each SnF6 unit of one chain is connected to a SnF6 unit of the second chain through a shared fluorine vertex. The single-crystal structure determination of [O2]­[Sn2F9]·0.9HF reveals that it is comprised of two-dimensional ([Sn2F9]−)∞ grids with [O2]+ cations and HF molecules located between them. The 2-D grids have a wavelike conformation. The ([Sn2F9]−)∞ layer contains both six- and seven-coordinated Sn­(IV) atoms that are interconnected by bridging fluorine atoms. A new, more complex [O2]+ salt, O2[Hg­(HF)]4[SbF6]9, was prepared. In its crystal structure, the Hg atoms bridge to SbF6 units to form a 3-D framework. The O2 + cations are located inside the voids while the HF molecules are bound to Hg atoms through the F atom. Attempts to prepare several chlorine analogues of O2 + fluorine salts (i.e., O2TiCl5 and O2MCl6 (M = Nb, Sb)) failed.

Reactions of ClF3 with Main Group and Transition Metal Oxides: Access to Dioxychloronium(V) Fluoridometallates and Oxidofluoridometallates

“…Only crystal structures with discrete [SiF 5 ] − anions have been reported for the homologous pentafluoridosilicate(IV) anion [73–76] . Whereas the homologous pentafluoridogermanate(IV) anion can either be discrete, as a [GeF 5 ] − anion in the 1,3‐bis(2,6‐diisopropylphenyl)imidazolium salt or a [Ge 3 F 16 ] 4− anion in [C(NH 2 ) 2 NH 3 ] 2 [Ge 3 F 16 ]⋅ n HF ( n =1, 2), or “polymerize” to form the anion [42,77,78] . The [GeF 6 ] polyhedra in the latter can either be trans ‐bridged to a linear chain as in [XeF 5 ][GeF 2/2 F 4/1 ] or cis ‐bridged to helical chains as in [ClO 2 ][GeF 2/2 F 4/1 ] or O 2 [GeF 5 ]⋅HF [42,78] .…”

“…Whereas the homologous pentafluoridogermanate(IV) anion can either be discrete, as a [GeF 5 ] − anion in the 1,3‐bis(2,6‐diisopropylphenyl)imidazolium salt or a [Ge 3 F 16 ] 4− anion in [C(NH 2 ) 2 NH 3 ] 2 [Ge 3 F 16 ]⋅ n HF ( n =1, 2), or “polymerize” to form the anion [42,77,78] . The [GeF 6 ] polyhedra in the latter can either be trans ‐bridged to a linear chain as in [XeF 5 ][GeF 2/2 F 4/1 ] or cis ‐bridged to helical chains as in [ClO 2 ][GeF 2/2 F 4/1 ] or O 2 [GeF 5 ]⋅HF [42,78] . For the Sn system, anions with higher Sn content such as [Sn 2 F 9 ] − and [Sn 5 F 24 ] 4− were described and they were either characterized by vibrational spectroscopy or single‐crystal X‐ray diffraction [78–80] .…”

“…The [GeF 6 ] polyhedra in the latter can either be trans ‐bridged to a linear chain as in [XeF 5 ][GeF 2/2 F 4/1 ] or cis ‐bridged to helical chains as in [ClO 2 ][GeF 2/2 F 4/1 ] or O 2 [GeF 5 ]⋅HF [42,78] . For the Sn system, anions with higher Sn content such as [Sn 2 F 9 ] − and [Sn 5 F 24 ] 4− were described and they were either characterized by vibrational spectroscopy or single‐crystal X‐ray diffraction [78–80] . The [Sn 2 F 9 ] − anion shows a ladder‐like structure motif in O 2 [Sn 2 F 9 ] and a more complex layer‐structure with hexa‐ and hepta‐coordinated Sn(IV) atoms in O 2 [Sn 2 F 9 ] ⋅ 0.9HF [78] .…”

“…For the Sn system, anions with higher Sn content such as [Sn 2 F 9 ] − and [Sn 5 F 24 ] 4− were described and they were either characterized by vibrational spectroscopy or single‐crystal X‐ray diffraction [78–80] . The [Sn 2 F 9 ] − anion shows a ladder‐like structure motif in O 2 [Sn 2 F 9 ] and a more complex layer‐structure with hexa‐ and hepta‐coordinated Sn(IV) atoms in O 2 [Sn 2 F 9 ] ⋅ 0.9HF [78] . Similar coordination numbers are observed for the Sn(IV) atoms in [XeF 5 ] 4 [Sn 5 F 24 ], in which the anion also forms a layer‐motif [80] …”

“…[73][74][75][76] Whereas the homologous pentafluoridogermanate(IV) anion can either be discrete, as a [GeF 5 ] À anion in the 1,3-bis(2,6-diisopropylphenyl)imidazolium salt or a [Ge 3 F 16 ] 4À anion in [C(NH 2 ) 2 NH 3 ] 2 [Ge 3 F 16 ]•nHF (n = 1, 2), or "polymerize" to form the 1 1 GeF 2=2 F 4=1 � � À anion. [42,77,78] The [42,78] For the Sn system, anions with higher Sn content such as [Sn 2 F 9 ] À and [Sn 5 F 24 ] 4À were described and they were either characterized by vibrational spectroscopy or single-crystal X-ray diffraction. [78][79][80] The , in which the anion also forms a layer-motif.…”