Control over Anion Coordination on Pd(II), Cu(I), and Ag(I) with Regioisomeric Phosphine‐Carboxylate Ligands.

The coordination of anionic donors is involved at various stages of catalytic cycles in transition‐metal catalysis, but control over the spatial positioning of anions around a metal center is a challenge in coordination chemistry. Here we show that regioisomeric phosphine‐carboxylate ligands provide spatial anion control on palladium(II) centers by favoring either κ2, cis‐κ1, or trans‐κ1 coordination of the carboxylate donor. Additionally, the palladium(II) carboxylates, which contain a methyl donor, upon protonation, deliver metal‐alkyl complexes that feature a coordinated carboxylic acid. Such complexes can be considered as models for the minima that follow the concerted metalation‐deprotonation transition state for C−H activation. The predictability of the coordination modes is further demonstrated on silver(I) and copper(I) centers, for which less common structures of mononuclear and dinuclear complexes can be obtained by using spatial anion control. Our results demonstrate the potential for spatial control over carboxylate anions in coordination chemistry. [ABSTRACT FROM AUTHOR]