Synthesis and Lewis Acid Properties of Neutral Silver(III) Adducts Containing the Ag(CF) Moiety.

The acetonitrile Ag complex [Ag(CF)(NCCH)] (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(CF)Cl] (3⋅) or [Ag(CF)] (1) via halide abstraction using AgNO or acidic treatment, resp. These two synthetic routes are herein reinvestigated.

Cross-Coupling Reactions Enabled by Well-Defined Ag(III) Compounds: Main Focus on Aromatic Fluorination and Trifluoromethylation.

Ag compounds are considered strong oxidizers of difficult handling. Accordingly, the involvement of Ag catalysts in cross-coupling via 2e redox sequences is frequently discarded. Nevertheless, organosilver(III) compounds have been authenticated using tetradentate macrocycles or perfluorinated groups as supporting ligands, and since 2014, first examples of cross-coupling enabled by Ag /Ag redox cycles saw light.

Electrophilicity of neutral square-planar organosilver(III) compounds.

Neutral Ag(III) complexes stabilised with just monodentate ligands are here unambiguously established. In a series of square-planar (CF)Ag(L) compounds with hard and soft Group 15 donor ligands, L, the metal center has been found to exhibit substantial acidity favouring apical coordination of an additional ligand under no coordination constraints.

Cross-Coupling through Ag(I)/Ag(III) Redox Manifold.

In ample variety of transformations, the presence of silver as an additive or co-catalyst is believed to be innocuous for the efficiency of the operating metal catalyst. Even though Ag additives are required often as coupling partners, oxidants or halide scavengers, its role as a catalytically competent species is widely neglected in cross-coupling reactions. Most likely, this is due to the erroneously assumed incapacity of Ag to undergo 2e redox steps.