Here we report the synthesis and characterization of a series of palladium β-diiminate complexes. Chloro-bridged dimers [Pd(Ar 2 nacnac)(μ-Cl)] 2 (where [Ar 2 nacnac] − is [(ArNC(CH 3 )) 2 CH] − with Ar being aryl substituents) can serve as versatile starting materials, and can be cleaved by neutral monodentate ligands (L) to form mononuclear complexes [Pd(Ar 2 nacnac)(L)Cl], or engage in unusual transmetallation reactions with boronic acids to form tetrapallada-macrocycles. The reactivity of the tetrapallada-macrocyclic complexes towards L-type ligands, as well as the reactivity of Pd(Ar 2 nacnac)(L)Cl] complexes towards boronic acids was also explored.