Coordination of noble metals by an ambiphilic PBiP pincer ligand: Metallophilic Bi–Cu and Bi–Ag interactions

Abstract Reaction of the pincer ligand PBiP with MCl (M = Cu, Ag) led to the complexes [M(μ-Cl)(PBiP)] 2 featuring M⋯Bi interactions, which were shown by DFT/NBO to have predominantly Bi → M character. In the series of compounds [Cu(μ-Cl)(PBiP)] 2 , [Ag(μ-Cl)(PBiP)] 2 and [AuCl(PBiP)] the ratios between the M–Bi distances and the covalent/van der Waals radii decrease, which indicates a strengthening of the interactions. Employing metal precursors with weakly interacting anions leads, according to NMR spectroscopic results, to monomeric complexes, which, however, aggregate in course of the crystallization process to give [M(anion)(PBiP)] x .