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 24 h 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[(κ2-C,N-Pd{(C10H6)–CH2–NCH–(2,6-Cl2C6H3)}]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[κ2-C,N-Pd{(C10H6)–CH2–NCH–(2,6-Cl2C6H3)}]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-d5 and PPh3 yielded the mononuclear compounds trans-N,L-[κ2-C,N-Pd{(C10H6)–CH2–NCH–(2,6-Cl2C6H3)}(X)(L)]; 4 (X = OAc, L = py-d5), 5 (X = OAc, L = PPh3), 6 (X = Cl, L = py-d5), 7 (X = Cl, L = PPh3), in which the imine ligands adopted the Z configuration. In addition, 3 reacted with diphenylacetylene, which afforded the mononuclear organopalladium compound [κ2-N,C1-η2-C3,C4-Pd{(PhCCPh)2–C10H6–CH2–NCH–(2,6-Cl2C6H3)}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·CH2Cl2 has been determined.