Reaction of the Schiff base ligand 1, 3, 3 C 6 H 2 C(H)dNCH 2 ] 2 C 6 H 4 (1) with palladium(II) acetate in toluene gave the doubly cyclometalated complex [1,3, 3 C 6 HC(H)dNCH 2 ](µ-O 2 CMe)} 2 C 6 H 4 ] (2), in which the two palladium atoms are intramolecularly bonded by acetato bridging ligands. The crystal structure of 2 is given. Reaction of the Schiff base ligand 1,4-[2,3,4-(MeO) 3 C 6 H 2 C(H)dNCH 2 ] 2 C 6 H 4 ( 6) with palladium(II) acetate under similar reaction conditions yielded the cyclometalated complex [1,3, Reaction of 2 and 7 with aqueous sodium chloride gave the chloro-bridged complexes [1,3, 8), respectively, after a metathesis reaction. Treatment of complex 2 with Ph 2 P(CH 2 ) 3 PPh 2 (dppp) in a 1:1 molar ratio gave the dinuclear cyclometalated complex [1,3, 3 C 6 HC(H)dNCH 2 ](OAc)} 2 C 6 H 4 (µ-Ph 2 P(CH 2 ) 3 PPh 2 )] (4), in which the metal atoms are bonded by the diphosphine ligand. Treatment of the chloro-bridged complex 3 with dppp in a 1:2 molar ratio gave the dinuclear cyclometalated complex [1,3, 3 C 6 HC(H)dNCH 2 ](Cl)} 2 C 6 H 4 (µ-Ph 2 P(CH 2 ) 3 PPh 2 )] ( 5), with the palladium atoms intramolecularly bridged by the diphosphine. The complex showed a fluxional behavior in solution, with the cyclometalated moieties adopting a cis/trans arrangement. Reaction of the chloro-bridged complex 8 with dppp in a 1:2 molar ratio yielded the mixture of complexes [1,3, 3 C 6 HC(H)dNCH 2 ](Cl)} 2 C 6 H 4 (µ-Ph 2 P(CH 2 ) 3 PPh 2 )] ( 9) and [1,3, 3 C 6 HC(H)dNCH 2 ](Cl)} 2 C 6 H 4 (µ-Ph 2 P(CH 2 ) 3 PPh 2 )] 2 (10), of which only 9 was isolated pure. Compound 9 showed a structure and solution behavior similar to those of 5; however, the structure of 10 was not unambiguously established. The crystal structure of 9 is also reported.
