Ferrocenyloximes of general formula [{(η 5 -C 5 H 4 )-C(R)=N(OH)}Fe(η 5 -C 5 H 5 )}] with R = H (1a) or CH 3 (1b) react at room temperature in methanol with Na 2 [PdCl 4 ] and Na(CH 3 COO) 3H 2 O in a 1:1:1 molar ratio producing the di-μ-chloro-bridged derivatives [Pd{[(η 5 -C 5 H 3 )-C(R)=N(OH)]Fe(η 5 -C 5 H 5 )}(μ-Cl)] 2 (with R = H (2a) or CH 3 (2b)) which undergo cleavage of the Pd(μ-Cl) 2 Pd units in the presence of PPh 3 to give the mononuclear cyclopalladated complexes [Pd{[(η 5 -C 5 H 3 )-C(R)=N(OH)]Fe(η 5 -C 5 H 5 )}Cl(PPh 3 )] (with R = H (3a) or CH 3 (3b)). The molecular structure of compound 3b has been determined by X-ray crystallography: monoclinic, space group C2c with a = 27.485(5) 9; b = 9.964(2) 9; c = 24.778(4) 9 and β = 131.07(3)°. These studies confirm the presence of a five-membered palladacycle fused with the C 5 H 3 ring of the ferrocenyl moiety, and a trans arrangement of the phosphine and the nitrogen.