Reaction of the thiosemicarbazone ligands C 4 H 4 NC(H)ϭ NN(H)C(S)NHR (R ϭ Me, a; Et, b) with Li 2 [PdCl 4 ] gave the dinuclear complexes [Pd{C 4 H 4 NC(H)ϭNNC(S)NHR}(μ-Cl)] 2 (R ϭ Me, 1a; Et, 1b) with a central Pd 2 Cl 2 core and with deprotonation of the thiosemicarbazones at the hydrazinic nitrogen atom. Treatment of 1a and 1b with triphenylphosphine gave the mononuclear compounds [Pd{C 4 H 4 C(H)ϭNNC(S)NHR}(Cl)(PPh 3 )] (R ϭ Me, 2a; Et, 2b), whereas reaction of 1a and 1b with tertiary diphosphines gave mono-and dinuclear compounds, as appropriate, with the 2197 corresponding diphosphine acting as a monodentate (6b), chelating (3a) and bridging ligand ( 4a, 5a, 4b, 5b). Treatment of 1a and 1b with (Ph 2 PCH 2 CH 2 PPh 2 )W(CO) 5 gave the new heterobimetallic complexes 7a and 7b. The crystal structures of complexes 3a and 4a are described.