Synthesis and Lewis Acid Properties of Neutral Silver(III) Adducts Containing the Ag^III(CF₃)₃ Moiety

The acetonitrile Ag^III complex [Ag^III(CF₃)₃(NCCH₃)] (2) has been reported independently by Eujen and Naumann in the last century, albeit with intriguing NMR discrepancy. In their reports, 2 was claimed to be obtained starting from either [Ag^III(CF₃)₃Cl]^- (3⋅_Cl) or [Ag^III(CF₃)₄]^- (1) via halide abstraction using AgNO₃ or acidic treatment, resp. These two synthetic routes are herein reinvestigated. The feasibility of Naumann's method is demonstrated, thus providing 2 yet accompanied by its s-triazinyl derivative [Ag^III(CF₃)₃(C₆H₉N₃)] (2'). The formation of 2' is unprecedented and was thereby investigated. Both 2 and 2' were isolated in pure fashion and fully characterized. In turn, halide extraction from 3⋅_Cl leads to the Ag^III-ONO₂ anion 5 instead of 2, as evidenced by NMR spectroscopy, EA and Sc-XRD.