Cyclopalladated compounds with a bidentate [C, N]/terdentate [C, N, S] benzylidenethiophene imine ligand. Crystal and molecular structures of [Pd{2,3-(MeO)2C6H2C(H)NCH2(C4H3S)}(μ-OAc)]2, [Pd{2,3-(MeO)2C6H2C(H)NCH2(C4H3S)}(Cl)·(PPh3)] and [{Pd[2,3-(MeO)

Reaction of the Schiff base ligand 2,3-(MeO)2C6H3C(H)NCH2(C4H3S) (1), with palladium(II) acetate in toluene gave the dinuclear cyclometallated complex [Pd{2,3-(MeO)2C6H2C(H)NCH2(C4H3S)}(μ-OAc)]2 (2), with the ligand bonded to the palladium atom through the imine nitrogen and the C6 carbon atom. The X-ray crystal structure of complex 2 is described. The reaction of 2 with aqueous sodium chloride gave the chloro-bridged complex [Pd{2,3-(MeO)2C6H2C(H)NCH2(C4H3S)}(μ-Cl)]2 (3), after a metathesis reaction. Reaction of 3 with PPh3 in acetone gave the mononuclear cyclometallated complex [Pd{2,3-(MeO)2C6H2C(H)NCH2(C4H3S)}(Cl)(PPh3)] (4), in a bridge-splitting reaction. Treatment of 4 with silver triflate gave the cyclometallated complex [Pd{2,3-(MeO)2C6H2C(H)NCH2(C4H3S)}(PPh3)][CF3SO3] (7), with the palladium atom bonded to four different atoms C, N, S and P. Reaction of 3 with the diphosphines dppp and dppb in a 1:1 molar ratio gave the dinuclear cyclometallated complexes [{Pd[2,3-(MeO)2C6H2C(H)NCH2(C4H3S)](Cl)}2(μ-Ph2P(CH2)nPPh2)] (5: n=3; 6: n=4), with the diphosphine bridging the two palladium atoms. The X-ray crystal structures of complexes 4 and 6 are reported.