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), O2MIV2F9 (M = Sn), O2MVF6 (M = As, Sb, Au, Pt), O2MV2F11 (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.
Highlights
Dioxygenyl salts are useful reagents for the oxidation of organic compounds to the corresponding cation radicals.[1,2] TheO2AsF6 C5F5N toanCd6F6O+,2SybieFld[6] inagre[Cc6aFp6a]b+[leMFo6f]−ox(iMdiz=ingAs,CS6bF)63,4anodr [C6F5N]+[MF6]− (M = As),[5] respectively
The reported syntheses of O2BF4 include the reaction between BF3 and O2F2.28 The resulting O2BF4 salt decomposes above 0 °C
When the synthesis is done in liquid anhydrous hydrogen fluoride (aHF) in a from tetrafluoroethylene-hexafluoropropylene blockcopolymer (FEP) reaction vessel (Table 1), the volatile compounds can be pumped away at low temperature and pure O2BF4 can be recovered in a quantitative yield (Figure S1, see the Supporting Information)
Summary
Dioxygenyl salts are useful reagents for the oxidation of organic compounds to the corresponding cation radicals.[1,2] The. O2AsF6 C5F5N toanCd6F6O+,2SybieFld[6] inagre[Cc6aFp6a]b+[leMFo6f]−ox(iMdiz=ingAs,CS6bF)63,4anodr [C6F5N]+[MF6]− (M = As),[5] respectively. [C6F5X]+, X = H, CF3 or C6F5; [1,4-C6F4(CF3)2]+; [2,3,5,6C6F4X2]+, X = H or CF3; [2,4,6-C6H3F3]+; [1,2,4,5-C6H2Cl4]+) as [AsF6]−, [SbF6]−, or [Sb2F11]− salts have been reported.[6,7] Other examples include the preparation of tertiary amine cation radicals[8] and the oxidations of N,N,N,N-. Octane, and 1,5-dithiacyclooctane to the corresponding radical cations as shown by EPR spectroscopy.[9] The reaction of (CF3)2NO with O2SbF6 produces CF3 radicals at low temperature.[10] Displacement reactions between O2MF6 and suitable amphoteric molecules produce free O2F radicals which generate atomic fluorine in situ upon decomposition.[11] A onestep reaction between carbon monoxide and dioxygenyl salts yields oxalyl fluoride [FC(O)C(O)F].12. A onestep reaction between carbon monoxide and dioxygenyl salts yields oxalyl fluoride [FC(O)C(O)F].12 The removal of radon and radioactive noble gas isotopes of xenon from contaminated atmospheres through the use of O2SbF6 was studied.[13,14] The reactivity of azides toward various dioxygenyl salts was investigated in the scope of research on highly energetic materials.[15]
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