Reaction of the Schiff base ligand derived from 4-pyridinecarboxaldehyde NC 5 H 4 C(H)N[2′,4′,6′-(CH 3 )C 6 H 2 ], (1), with palladium(II) acetate in toluene at 60°C for 24h gave [Pd{NC 5 H 4 C(H)N[2′,4′,6′-(CH 3 )C 6 H 2 ]} 2 (OCOCH 3 ) 2 ], (2), with two ligands coordinated through the pyridine nitrogen. Treatment of the Schiff base ligand derived from 4-pyridinecarboxaldehyde N-oxide, 4-(O)NC 5 H 4 C(H)N[2′,4′,6′-(CH 3 )C 6 H 2 ], (4), with palladium(II) acetate in toluene at 75°C gave the dinuclear acetato-bridged complex [Pd{4-(O)NC 5 H 3 C(H)N[2′,4′,6′-(CH 3 )C 6 H 2 ]}(OCOCH 3 )] 2 , (5) with metallation of an aromatic phenyl carbon. Reaction of complex 5 with sodium chloride or lithium bromide gave the dinuclear halogen-bridged complexes [Pd{4-(O)NC 5 H 3 C(H)N[2′,4′,6′-(CH 3 )C 6 H 2 ]}(Cl)] 2 , (6) and [Pd{4-(O)NC 5 H 3 C(H)N[2′,4′,6′-(CH 3 )C 6 H 2 ]}(Br)] 2 , (7), after the metathesis reaction. Reaction of 6 and 7 with triphenylphosphine gave the mononuclear species [Pd{4-(O)NC 5 H 3 C(H)N[2′,4′,6′-(CH 3 )C 6 H 2 ]}(Cl)(PPh 3 )], (8) and [Pd{4-(O)NC 5 H 3 C(H)N[2′,4′,6′-(CH 3 )C 6 H 2 ]}-(Br)(PPh 3 )], (9), as air stable solids. Treatment of 6 and 7 with Ph 2 P(CH 2 ) 2 PPh 2 (dppe) in a complex/diphosphine 1:2 molar ratio gave the mononuclear complexes [Pd{4-(O)NC 5 H 3 C(H)N[2′,4′,6′-(CH 3 )C 6 H 2 ]}(PPh 2 (CH 2 ) 2 PPh 2 )][Cl], (10), and [Pd{4-(O)NC 5 H 3 C(H)N[2′,4′,6′-(CH 3 )C 6 H 2 ]}(PPh 2 (CH 2 ) 2 PPh 2 )][PF 6 ], (11), with a chelating diphosphine. The molecular structure of complex 9 was determined by X-ray single crystal diffraction analysis.