The reaction of the Schiff base ligands 1,3-[CN(H)CH2C4H7O]2C6H4 (1) and 1,4-[CN(H)CH2C4H7O]2C6H4 (14) with palladium(II) acetate in toluene gave the acetato-bridged cyclometallated compounds [Pd2{1,3-[C(H)NCH2C4H7O]2C6H2}(μ-AcO)2]2 (2) and [(μ-AcO)Pd{1,4-[C(H)NCH2C4H7O]2C6H2}Pd(μ-AcO)]n (15). Reaction of 2 and 15 with aqueous sodium chloride gave the chloro-bridged cyclometallated compounds [Pd2{1,3-[C(H)NCH2C4H7O]2C6H2}(μ-Cl)2]2 (3) and [(μ-Cl)Pd{1,4-[C(H)NCH2C4H7O]2C6H2}Pd(μ-Cl)]n (16), respectively, after a metathesis reaction. Reaction of 3 with triphenylphosphine in a 1∶2 molar ratio gave the tetranuclear complex [Pd2{1,3-[C(H)NCH2C4H7O]2C6H2}(μ-Cl)(Cl)(PPh3)]2 (4), where only one of the bridging PdCl2Pd moieties was cleaved, and which was characterized by X-ray crystal structure analysis. However, reaction of 16 with PPh3 gave the dinuclear complex [(PPh3)(Cl)Pd{1,4-[C(H)NCH2C4H7O]2C6H2}Pd(PPh3)(Cl)] (17) after a full bridge-splitting reaction. Similarly, treatment of 3 with PMe2Ph, pyridine and thallium acetylacetonate produced the dinuclear complexes 5, 6 and 7, respectively. Treatment of 4 with pyridine in a 1∶2 molar ratio, and with 4,4′-dipyridyl in an 1∶1 molar ratio, gave the di- and tetranuclear complexes 12 and 13, respectively. Reaction of 3 with the tertiary diphosphine cis-Ph2PCHCHPPh2 in a 1∶2 molar ratio yielded the tetranuclear complex [Pd2{1,3-[C(H)NCH2C4H7O]2C6H2}(μ-Cl)(Ph2PCHCHPPh2-P,P)][Cl]2 (8) after selective splitting of one of the PdCl2Pd bridging moieties. However, reaction of 3 with cis-Ph2PCHCHPPh2 and Ph2P(CH2)2PPh2 in 1∶4 molar ratios gave the dinuclear complexes 9 and 10, respectively. Reaction of 3 with the diphosphine Ph2PC5H4FeC5H4PPh2 in a 1∶2 molar ratio yielded the trinuclear complex [Pd2{1,3-[C(H)NCH2C4H7O]2C6H2}(μ-Ph2PC5H4FeC5H4PPh2)] (11), with the diphosphine bridging the two palladium atoms of the dicyclometallated moiety.