Silver Salts of the Weakly Coordinating Anion [Me 3 NB 12 Cl 11 ] –

Silver(I) salts of weakly coordinating anions (WCA) are commonly applied as oxidizing agents or halide abstracting reagents. The feasibility of a particular silver salt for such applications strongly depends on the “nakedness“ of the silver cation. In this study the reactivity of Ag[Me 3 NB 12 Cl 11 ] in different solvents was investigated. Crystal structures of a variety of complexes were obtained. In several crystal structures two boron clusters are bridged by Ag–Cl contacts. This leads to polymeric structures (e.g. for Ag[Me 3 NB 12 Cl 11 ]·0.5CH 2 Cl 2 and Ag[Me 3 NB 12 Cl 11 ]·SO 2 ). Sterically demanding aromatics like mesitylene, pyrene, and acenaphthene are η 1 ‐ or η 2 ‐bonded to the silver atom and also form coordination polymers, whereas benzene as a ligand leads to a molecular structure, in which two benzene molecules are η 2 ‐coordinated to the silver cation. In contrast, strong σ donor ligands like pyridine and triphenylphosphine give homoleptic silver complexes and thus cation and anion are separated. Furthermore, the ability of Ag[Me 3 NB 12 Cl 11 ] for performing metathesis reactions was investigated. The reaction with Au I Cl gave the [Au(NCMe) 2 ] + cation.