Syntheses of Dioxygenyl Salts by Photochemical Reactions in Liquid Anhydrous Hydrogen Fluoride: X-ray Crystal Structures of ?- and ?-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), 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, ?-O2Sn2F9 (1-D), and the HF-solvated and nonsolvated forms of ?-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 ?-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.

SUBMITTER: Mazej Z 

PROVIDER: S-EPMC7307900 | biostudies-literature | 2020 Feb

REPOSITORIES: biostudies-literature