Probing the Reactivity of the Potent AgF2 Oxidizer. Part 1: Organic Compounds

Abstract

The reactivity of Ag(II)F 2 towards a variety of organic compounds of a high degree of fluorination has been investigated. AgF 2 readily fluorinates P(C 6 F 5 ) 3 to PF 2 (C 6 F 5 ) 3 , and attacks the isothiocyanate functional group, -NCS, yielding Ag 2 S. Perfluorinated aliphatic nitriles resist the action of AgF 2 , but aromatic C 6 F 5 CN undergoes a radical-initiated oligomerization; byproducts include C 6 F 6 CN • and C 6 F 5 N 2 • (after intramolecular rearrangement following the bimolecular reaction). AgF 2 oxidizes higher fluorosulfonic acids (C 4 F 9 SO 3 H, C 8 F 17 SO 3 H) at or close to the room temperature and triflic acid (CF 3 SO 3 H) at its boiling point to the corresponding peroxides. CF 3 COOH and CF 3 CONH 2 are also decomposed in redox reactions, but the gaseous products have not been identified. Surprisingly, AgF 2 is kinetically inert to perfluorinated aromatic hydrocarbons and to CCl 4 , but it decomposes CBr 4 with vigorous elimination of Br 2 . CI 4 decomposes explosively in the presence of AgF 2 . C 6 F 5 OH and CF 3 COOH are readily oxidized with AgF 2 but, surprisingly, t -C 4 F 9 OH is kinetically resistant under similar conditions. Coordination complexes of perfluorinated aza and oxa Lewis bases (including perfluorinated 15-crown-5 ether) and AgF 2 are not formed under the experimental conditions.