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

Abstract

The acetonitrile AgIII complex [AgIII(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 [AgIII(CF3)3Cl]– (3.Cl) or [AgIII(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 [AgIII(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 AgIII‐ONO2 anion 5 instead of 2, as evidenced by NMR spectroscopy, EA and Sc‐XRD.