Abstract The complex O3ClOPd(C6F5)(PPh3)2 has proved to be a fairly effective intermediate for the synthesis of cationic derivatives of Pd(II), since the perchlorato ligand shows a poor coordination capacity and is therefore easily displaced by neutral ligands. In this way cationic complexes of the [LPd(C6F5)(PPh3)2]ClO4 type have been prepared, where L[dbnd]PPh3, PEt3, PBu3, C5H5N, AsPh3, HN(CH2-CH2-CH3)2, H2O, O2NCH3, ONC5H4.C6H5, OPPh3 or SPPh3.