Collect. Czech. Chem. Commun. 2008, 73, 1729-1746

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

Dorota Grzybowskaa, Przemysław Malinowskia, Zoran Mazejb and Wojciech Grochalaa,c,*

a Laboratory of Intermolecular Interactions, Faculty of Chemistry, University of Warsaw, Pasteur 1, 02093 Warsaw, Poland
b Department of Inorganic Chemistry and Technology, Jožef Stefan Institute, Jamova 39, SI-1000 Ljubljana, Slovenia
c Laboratory of Technology of Novel Functional Materials, Interdisciplinary Center for Mathematical and Computational Modeling, University of Warsaw, Pawińskiego 5a, 02106 Warsaw, Poland


The reactivity of Ag(II)F2 towards a variety of organic compounds of a high degree of fluorination has been investigated. AgF2 readily fluorinates P(C6F5)3 to PF2(C6F5)3, and attacks the isothiocyanate functional group, -NCS, yielding Ag2S. Perfluorinated aliphatic nitriles resist the action of AgF2, but aromatic C6F5CN undergoes a radical-initiated oligomerization; byproducts include C6F6CN and C6F5N2 (after intramolecular rearrangement following the bimolecular reaction). AgF2 oxidizes higher fluorosulfonic acids (C4F9SO3H, C8F17SO3H) at or close to the room temperature and triflic acid (CF3SO3H) at its boiling point to the corresponding peroxides. CF3COOH and CF3CONH2 are also decomposed in redox reactions, but the gaseous products have not been identified. Surprisingly, AgF2 is kinetically inert to perfluorinated aromatic hydrocarbons and to CCl4, but it decomposes CBr4 with vigorous elimination of Br2. CI4 decomposes explosively in the presence of AgF2. C6F5OH and CF3COOH are readily oxidized with AgF2 but, surprisingly, t-C4F9OH is kinetically resistant under similar conditions. Coordination complexes of perfluorinated aza and oxa Lewis bases (including perfluorinated 15-crown-5 ether) and AgF2 are not formed under the experimental conditions.

Keywords: Acid-base reactions; Fluorine; Fluorination; Redox reactions; Oxidations; Silver.

References: 34 live references.