The reaction of (Z)-4-aminopent-3-en-2-one with different chlorodiorganylphosphanes established three new ligands composed of a hard and soft coordination site. The soft phosphane site is easily coordinated to palladium(II) as a first step in the potential formation of heterodinuclear complexes. Surprisingly, the formed square-planar dichloridopalladium(II) complexes exhibit exclusively trans configuration. A cis configurated palladium(II) complex can be formed, when the linker between the phosphane and the enaminoketone unit is enlarged and allows more flexibility. The reaction between (Z)-4-(2'-hydroxyethylamino)pent-3-en-2-one and chlorodiorganylphosphanes revealed two new ligands that coordinate to palladium(II). With phenyl substituents at the phosphorus atom a cis palladium complex was obtained, whereas for isopropyl substituents a trans complex was formed. Molecular structures of all complexes were analyzed by single-crystal X-ray diffraction.