Hydrogen Bond Networks in Five- and Eight-membered Palladium and Platinum Complexes derived from bis(2-aminophenyl)ether and bis(2-aminophenyl)thioether ligands.

The reaction of [MII(MeCN)2Cl2] (M = Pd, Pt) with the diamino ligands either bis(2-aminophenyl)ether or bis(2-aminophenyl)thioether {(NH2-C6H4)2D} [D = O (L1); D = S (L2)] yielded neutral coordination complexes of general formulae [M(Ln)Cl2] [M = Pd, n = 1 (1); Pt, n = 1 (2); Pd, n = 2 (3); Pd, n = 2 (4); Pt, n = 2 (5). The reaction of L2 with K2[PtCl6] promoted the mono-deprotonation of the diamino ligand to yield the neutral complex [PtIV{(NH2-C6H4)S(NH-C6H4)}Cl3] (6); when the H2[PtCl6] acid was used an ionic complex [PtIV(L2)Cl3]Cl (7) was obtained. All complexes were characterized by NMR in solution, vibrational spectroscopy, and by X-ray diffraction studies. The molecular structures of the complexes revealed different coordination patterns of the diamino ligands; L1 just displayed a ?2N mode meanwhile L2 exhibited a wide variety of patterns (?2N, ?N?S, and ?2N?S) forming chelate rings of five- or eight-members. The presence of N?H functions in the ligand moieties enhanced the formation of extended hydrogen-bond networks; these supramolecular arrangements were mainly discussed at unitary and binary levels and sorted according to the molecular coordination patterns observed.