The reaction of the thiosemicarbazones (η 5 -C 5 H 5 )Fe(η 5 -C 5 H 4 )C(H)NN(H)C(S)NHR (R=H, a; R=Me, b) with K 2 PdCl 4 afforded octanuclear cyclometallated complexes [Pd{(η 5 -C 5 H 5 )Fe(η 5 -C 5 H 3 )C(H)NNC(S)NHR}] 4 (R=H, 1a; R=Me, 1b). Reaction of complexes 1a and 1b with tertiary diphosphines in 1:2 molar ratio and subsequent recrystallization from CH 2 Cl 2 /n-C 6 H 14 gave rise to tetranuclear complexes [{Pd[(η 5 -C 5 H 5 )Fe(η 5 -C 5 H 4 )C(H)NNC(S)NHR](Cl)} 2 (μ-Ph 2 P(CH 2 ) n PPh 2 )] (R=H, n=4, 2a; R=Me, n=1, 2b; n=4, 3b). Treatment of complexes 1a and 1b with tertiary monophosphines in 1:4 molar ratio and subsequent recrystallization from CH 2 Cl 2 /n-C 6 H 14 gave rise to dinuclear complexes [Pd{(η 5 -C 5 H 5 )Fe(η 5 -C 5 H 4 )C(H)NNC(S)–NHR}(Cl)(P)] (R=H: P=PPh 3 , 3a; P=PPh 2 Et, 4a; P=P(C 6 D 5 ) 3 , 5a; R=Me: P=PPh 3 , 4b; P=PPh 2 Et, 5b; P=P(C 6 D 5 ) 3 , 6b). The crystal structures of 2a and 2b have been determined by X-ray crystallography.