The reaction of [(Cp)Fe{(η⁵-C₅H₄)-CH=N-(CH₂)^n-(C₄H₃S)}] {Cp = (η⁵-C₅H₅) and n = 1 (1b) or 2 (1c)} with Na₂[PdCl₄] and NaAcO.3H₂O gave [(Cp)Fe{(η-η⁵-Fe-η¹-Pd-C₅H₃)-CH=N-(CH₂)^n-(C₄H₃S)}Cl] {n = 1 (2b) or 2 (2c)} with a [C(sp²,ferrocene),N,S(thienyl)]^– ligand. The study of the reactivity of 2b or 2c with PPh₃ under different experimental conditions has afforded the isolation of [(Cp)Fe{(η-η⁵-Fe-η¹-Pd-C₅H₃)-CH=N-(CH₂)^n-(C₄H₃S)}Cl(PPh₃)] {n = 1 (3b) or 2 (3c)} and [(Cp)Fe{(η-η⁵-Fe-η¹-Pd-C₅H₃)-CH=N-(CH₂)^n-(C₄H₃S)}(PPh₃)][BF₄] {n = 1 (4b) or 2 (4c)} where 1b or 1c behave as a bidentate [C(sp²,ferrocene),N]^– (in 3b and 3c) or as a terdentate [C(sp²,ferrocene),N,S(thienyl)]^– (in 4b and 4c) ligand. The crystal structures of 3b.1/2CH₂Cl₂, 3c.2H₂O and 4c.CH₂Cl₂ confirm the mode of binding of the ligands. The results obtained from these studies and the solution behavior of 4b and 4c reveal that the σ(Pd-S) bond of 2b, 2c, 4b and 4c is more labile that in [(Cp)Fe{(η-η⁵-Fe-η¹-Pd-C₅H₃)-CH=N-(C₆H₄-2SMe)}Cl] or [(Cp)Fe{(η-η⁵-Fe-η¹-Pd-C₅H₃)-CH=N-(C₆H₄-2SMe)}(PPh₃)][BF₄] with a [C(sp²,ferrocene),N,S(thioether)]^– ligand.