The reaction of equimolecular amounts of (E)-N-(2,6-dichlorobenzylidene)(naphthalen-1-yl)methanamine (1) and Pd(OAc) 2 in acetic acid at 60°C for 24h produced a selective palladation at the 2 position of the naphthyl group of 1, which afforded the new acetato-bridged five-membered cyclopalladated dimer (μ-OAc) 2 [(κ 2 -C,N-Pd{(C 10 H 6 )–CH 2 –NCH–(2,6-Cl 2 C 6 H 3 )}] 2 (2), in which the imines adopted the Z configuration. A metathesis reaction between 2 and LiCl exchanged the acetato ligands of 2 for chloro ligands. This produced the dinuclear cyclopalladated compound (μ-Cl) 2 [κ 2 -C,N-Pd{(C 10 H 6 )–CH 2 –NCH–(2,6-Cl 2 C 6 H 3 )}] 2 (3), which consisted of a mixture of stereoisomers with imines in the E and Z configuration. Bridge-splitting reactions of the dimers 2 and 3 with py-d 5 and PPh 3 yielded the mononuclear compounds trans-N,L-[κ 2 -C,N-Pd{(C 10 H 6 )–CH 2 –NCH–(2,6-Cl 2 C 6 H 3 )}(X)(L)]; 4 (X=OAc, L=py-d 5 ), 5 (X=OAc, L=PPh 3 ), 6 (X=Cl, L=py-d 5 ), 7 (X=Cl, L=PPh 3 ), in which the imine ligands adopted the Z configuration. In addition, 3 reacted with diphenylacetylene, which afforded the mononuclear organopalladium compound [κ 2 -N,C1-η 2 -C3,C4-Pd{(PhCCPh) 2 –C 10 H 6 –CH 2 –NCH–(2,6-Cl 2 C 6 H 3 )}Cl] (8). This compound derived from the insertion of two alkyne molecules into the C–Pd σ bonds of 3 and presented the imine ligand in a Z configuration. The crystal structure of 8·CH 2 Cl 2 has been determined.