Multifaceted role of silver salts as ligand scavengers and different behavior of nickel and palladium complexes: beyond halide abstraction

Abstract

The reaction of [NiArBr(PPh₃)₂] with AgBF₄ brings about the abstraction of both the halide and phosphine from the nickel center by silver. When the reaction is carried out in CH₂Cl₂/toluene a mixture of the cationic aquo derivatives [NiAr(H₂O)(PPh₃)₂]BF₄ (2) and [NiAr(H₂O)₂(PPh₃)]BF₄ (3) is formed, along with AgBr and [Ag(PPh₃)_n]BF₄. When the same reaction is carried out in acetone as the solvent, it leads to the completely different complex [NiAr(κ²-O, O–MeC(O)CH₂C(OH)Me₂)(PPh₃)] (5), bearing a chelating ligand formed by the aldol self-condensation of acetone. Phosphine abstraction by silver is less favorable for the analogous palladium(II) complexes and only occurs if a large excess of AgBF₄ is used. Thus, silver salts can be safely used as halide scavengers for palladium derivatives. However, the generation of cationic Ni complexes from neutral precursors by halide extraction with a silver salt may produce naked species, different than those expected, and highly reactive in certain media.