A method for assignment of the relative stereochemistry in acyclic pi-allyl)palladium complexes by H-1 NMR H-H coupling constants has been developed. It is based on the introduction of nitrogen chelating ligands of the bipyridyl type into the complexes. The analytical suitability of several other types of nitrogen chelating ligands has also been investigated. A model for rationalization of the observed relation between stereochemistry and spectral parameters is proposed. Introduction of the chelating ligand also affects the syn,anti equilibrium of the complexes. Isomer ratios depend upon the relative stereochemistry of the side chain as well as on the chelating ligand.