14 mono-, di-, and tetranuclear palladium complexes were prepared to study the coordination chemistry of symmetrical and unsymmetrical azole-derived diimines and their anions. The diverse range of complexes obtained highlights the structural and electronic diversities imposed by these ligands. Using the monopalladium species, the electronic properties of selected bidentate ligands were determined, ranked, and compared by 13C NMR spectroscopy, extending the scope of the HEP2 (Huynh electronic parameter 2) scale, which can detect even subtle differences. Moreover, the %Vbur (percentage volume buried) values as an estimate for the steric bulk of some ligands were determined using the solid-state molecular structures of their complexes, and a preliminary stereoelectronic map was established.