The ligands ( S c, S p)-1-diphenylphosphino-2,1′-(1-dicyclohexylphosphinopropanediyl)ferrocene, ( S c, S p)-PP CyPF, and ( S c, S p)-1-diphenylphosphino-2,1′-(1-diphenylphosphinopropanediyl)ferrocene, ( S c, S p)-PP PhPF, have been used in the synthesis of the new Pd(0) and Pd(II) derivatives [Pd(PP CyPF)(DMFU)] ( 1) (DMFU = dimethylfumarate), [Pd(PP CyPF)(MA)] ( 2) (MA = maleic anhydride), [Pd(η 3-2-Me-C 3H 4)(PP)]OTf (PP = PP CyPF, 3; PP PhPF, 4) (OTf = triflate), [PdRR′(PP)] (R = Me, R′ = Cl, PP = PP CyPF, 5, PP PhPF, 6; R = R′ = Me, PP = PP CyPF, 7, PP PhPF, 8; R = R′ = C 6F 5, PP = PP CyPF, 9, PP PhPF, 10). The molecular structure of 7 has been determined by X-ray diffraction. In the cases of complexes 1– 4 two isomers are formed depending on the orientation of the ancillary ligand with respect to the ferrocenyl core. The stereochemistry of these complexes has been determined. In complex 6 the two possible isomers are obtained whereas in complex 5 the derivative with the Me group trans to PPh 2 is selectively formed. Restricted rotation of the pentafluorophenyl groups with respect to the Pd–C bond has been found in 9 and 10. In all derivatives the conformation of the ferrocenyl ligand is the same as that seen by X-ray diffraction and deduced from NMR data.