The oxidative addition reaction of 1,4-(C N(H)CH 2 CH 2 Me 2 ) 2 -2,5-Cl 2 C 6 H 2 with tris(dibenzylideneacetone)dipalladium(0) in benzene gave the doubly cyclometallated compound [(Cl)Pd{Me 2 NCH 2 CH 2 N (H)C}C 6 H 2 {C(H) NCH 2 CH 2 NMe 2 }Pd(Cl)] (1) with each palladium atom C,N,N' bonded to the ligand. Treatment of 1 with thallium acetylacetonate gave the dinuclear cyclometallated complex 2 with two chelating acetylacetonate ligands. Reaction of 1 with tertiary monophosphines in a 1-phosphine 1:2 molar ratio gave dinuclear cyclometallated complexes 3-7, in which the palladium NMe 2 bond has been broken, whereas treatment of 1 with silver perchlorate, followed by reaction with PPh 3 in a 1-phosphine 1:2 molar ratio gave cyclometallated complex 4 where the ligand remains C,N,N' bonded and the chloride ligand has been substituted by triphenylphosphine. Treatment of 1 with tertiary diphosphines leads to dinuclear compounds 8, 10 and 11, whilst previous treatment of 1 with silver perchlorate followed by the diphosphine 1,4-bis(diphenylphosphino)butane (dppb) in a 1-diphosphine 1:1 molar ratio yielded the tetranuclear complex 9. Reaction of 1 with the tertiary triphosphine bis(2-diphenylphosphinoethyl)phenylphosphine in 1:2 molar ratio gave the complex [{(Ph 2 PCH 2 CH 2 ) 2 PPh-P,P,P}Pd{Me 2 NCH 2 CH 2 N (H)C}-C 6 H 2 {C(H) NCH 2 CH 2 NMe 2 }Pd{(Ph 2 PCH 2 CH 2 ) 2 PPh-P,P,P}][Cl] 2 (12) in which both palladium atoms are pentacoordinated. The crystal structures of 1 and 12 are described.