A Versatile Silver(I) Pentafluorooxosulfate Reagent for the Synthesis of OSF5 Compounds

Herein, we report the preparation of silver(I) pentafluorooxosulfate from commercially available AgF and OSF4. The compound is surprisingly stable in a MeCN solution. Apart from that, AgOSF5 has been stabilised by the addition of 2,2′‐bipyridine ligands. Starting from solutions of the unstabilised silver(I) salt, OSF5 complexes with NiII, CuI, and CuII‐centres have been obtained. In addition, AgOSF5 has proven to be generally capable of mediating the transfer of OSF5 groups to aryne moieties, thus furnishing a new and safe method for the preparation of OSF5‐substituted arenes. X‐ray crystal structure analysis of selected transition‐metal OSF5 compounds have revealed distorted octahedral [OSF5]− anions which are extensively stabilised by hydrogen bonding. The reaction of AgF with SOF4 in MeCN solution gives rise to solvated AgOSF5, which defines the starting point for a variety of other SF5O compounds. For example, transition metal salts are accessible by metathesis; furthermore, bipyridine‐stabilised AgOSF5 has proven its general utility in the preparation of SF5O‐substituted aromatics. The solid‐state structure of the distorted octahedral [OSF5]− anion has been revealed by X‐ray crystallography.