The effects on ligands in nucleophilic reaction of eta(3)-allylpalladium chloride dimers were studied. Reaction of steroid 1 with Na2PdCl4 in concentrated HCl under CO gave the cis,trans-bis-mu-dichloro-eta(3)-allylpalladium complex 2 after recrystallization. Reaction of 2 with malonate anion in the presence of PPh3 afforded trans-3 in 65% yield. When Dppe was used, cis-3 was obtained as the major product. In nucleophilic reactions of bicyclic eta(3)-allylpalladium chloride complex 4a or 4b with PPh3, cis-5 was the major product. However, the reaction with Dppe gave trans-5 predominantly. The stereochemistry in the nucleophilic reaction of eta(3)-allylpalladium chloride dimer is dependent on the added phosphines.