Probing the Reactivity of the Potent AgF2 Oxidizer. Part 2: Inorganic Compounds

The reactivity of (AgF2)-F-II towards forty two inorganic compounds containing oxo- and chloro- ligands, has been investigated. Five families of compounds were studied: (i binary oxides of metals and nonmetals, (ii) ternary salts of inorganic oxo acids, (iii) concentrated or anhydrous oxo- acids, (iv) binary and ternary chlorides and (v) oxochlorides. At low temperatures up to 200 degrees C AgF2 readily oxidizes HgO, B2O3, PbO2, As2O5, Ag2SO4, LiBO2, K2CO3, KVO3, Ag2WO4, and AgMnO4 with concomitant oxygen evolution. In the same conditions V2O5, CrO3, MoO3, WO3, CuO, Tl2O3, I2O5, Re2O7, K2SO4, HgSO4, KSO3F, KNO3, KClO4, KIO4, BaCrO4, KMnO4 and KReO4 resist the action of AgF2 but many of these compounds get oxidized at higher temperatures (up to nearly 300 degrees C). Substantial inertness of sulfates, chromates, nitrates, perchlorates, permanganates and perrhenates suggests that one might attempt to synthesize salts of divalent silver with these anions. AgF2 vigorously reacts with H2SO4 (fuming, 30% SO3), HSO3Cl (100%), HClO4 (70%), and HNO3 (fuming, 100%) at room temperature yielding salts of Ag-I and O-2; for HClO4 and HNO3 pre-cooled to -35 degrees C metastable Perchlorate / nitrate complexes of Ag-II are obtained. Anhydrous HSO3F behaves similar to HSO3CF3 (see Part I of this series) yielding slow methathetical conversion of AgF2 without concomitant redox reaction. Majority of chlorides and oxochlorides studied (AgCl, AuCl3, KAuCl4, WCl6, WOCl4, MoOCl4, MoO2Cl2) react with AgF2 at temperatures below 160 degrees C. Reaction with SiCl4 (in contrast to CCl4) is violent and very exothermic at room temperature. Liquid CrO2Cl2 (at room temperature) and solid WO2Cl2 (UP to 180 degrees C) are kinetically inert to AgF2. We do not observe intercalation of AgF2 with various redox-inert oxo- and chloro- Lewis bases at the experimental conditions.