A series of ruthenium(II) complexes of polypicolylamine ligands have been prepared. The reaction of Ru(PhCN)(4)Cl-2 with the tridentate ligand N,N-bis(2-pyridylmethyl)aniline (phdpa) followed by precipitation with PF6- salts affords the complex, [Ru(phdpa)(2)](PF6)(2). The crystal structure of [Ru(phdpa)(2)](PF6)(2) shows that the ligand coordinates in a facial mode, with sp(3-) nitrogens located cis to each other. The reaction of Ru(dmso)(4)Cl-2 with the tetradentate ligand tris(2-pyridylmethyl)amine (tpa) in ethanol yielded the (Cl, N-amine)-trans [Ru(tpa)(dmso)Cl](PF6) complex which was characterized by X-ray crystallography. [Ru(tpa)(dmso)Cl](PF6) reacts with bipyridine, tpa and tricyanomethane anion (tcm) affording the [Ru(tpa)(bipy)](PF6)(2), [RU(tpa)(2)](PF6)(2) and Ru(tpa)(tcm)(2) complexes, respectively. The structures of [Ru(tpa)(bipy)(2)](PF6)(2) and Ru(tpa)(tcm)(2) show that tpa acts as a tetradentate ligand, while in [Ru(tpa)(2)](PF6)(2) it is tridentate, facially coordinated, with one non-coordinated pyridine. (C) 2003 Elsevier Science Ltd. All rights reserved.