A library of 12 palladium(II) complexes of the type [PdBr(iPr2-bimy)(L∧X)] comprising 10 dithiocarbamato (R2NCS2-) and two xanthato (ROCS2-) ligands have been prepared and fully characterized. With these complexes in hand, the electronic and steric properties of the bidentate, monoanionic ligands were evaluated using the HEP2 and %Vbur methodologies. Moreover, the construction of the first stereoelectronic map for dithiocarbamates enabled the in-principle identification of optimal ligand parameters for enhanced cytotoxic activities of their gold(III) complexes. This application of the stereoelectronic map showcases its viability as a useful tool to establish structure-activity relationships for rational ligand design.