The synthesis of new cyclometalated compounds of palladium(II) with the mixed-donor bidentate ligands o-Ph 2 PC 6 H 4 -CH=NR is described. Two series of complexes [Pd(C N )(o-Ph 2 PC 6 H 4 -CH=NR)][PF 6 ] have been prepared using either azobenzene or 2-phenylpyridine as cyclometalated ligands [C N =azobenzene (azb); R=Me (1a), Et (2a), n Pr (3a), i Pr (4a), t Bu (5a), Ph (6a), NH-Me (7a); C N =2-phenylpyridine (phpy); R=Me (1b), Et (2b), n Pr (3b), i Pr (4b), t Bu (5b), Ph (6b), NH-Me (7b)]. The new complexes were characterized by partial elemental analyses and spectroscopic methods (IR, FAB, 1 H and 3 1 P NMR). The molecular structures of compounds 2a (monoclinic, P 2 1 /n) and 1b (monoclinic, C 2/c) have been determined by a single-crystal diffraction study. In both cases this technique revealed the relative trans configuration between the phosphorus atom and the nitrogen atom of the ortho-metalated ligand.