Inorganic Chemistry, Vol.42, No.4, 960-969, 2003
Water displacement by cyanogold complexes in binuclear nickel(II) compounds based on bridging oxalate. Synthesis, structural diversity, magnetic properties, and DFT calculations
Several cyanogold complexes react with the binuclear nickel complex [{Ni(dien)(H2O)}(2)(mu-ox)](PF6)(2).2H(2)O to give the compounds [{Ni(dien)(H2O)}(2)(mu-ox)]Br-2 (1), [{Ni(dien)(Au(CN)(2))}(2)(mu-ox)] (2), and [{Ni(dien)}(2)(mu-ox){mu-Au(CN)(4)}](PF6) (3) (dien, diethilenetriamine; ox, oxalate). In the case of compounds 2 and 3, water displacement by the corresponding cyanogold complex takes place, whereas compound 1 is formed by a substitution of the anion. The crystal structures of compounds 1 and 2 present a 2D arrangement where the layers are connected by van der Waals forces (1) or N-H...NdropC hydrogen bonds (2), where each binuclear complex is hydrogen bonded to its neighbors, whereas compound 3 presents a novel structure where the tetracyanoaurate acts as a bridging ligand to give a polymeric compound. Magnetic studies of these compounds reveal an antiferromagnetic behavior. Finally, density functional theory (DFT) calculations have been performed on isolated models of compounds 2 and 3 in order to gain some insight about the different behavior of the [Au(CN)(2)](-) and [Au(CN)(4)](-) groups as ligands and proton acceptors in hydrogen bonds.