Crystal structures and substitution reactions of trans(O,S)-[Ru(bpy) Cl(dmso-S)_2(OH_2)]~+ and three derivative complexes, trans(L,S)-[Ru(bpy)Cl(dmso-S)_2(L)]~+ (bpy: 2,2'-bipyridine, dmso: Dimethyl sulfoxide, L = dmso-O, MeOH, or MeCN)

摘要

The labile cationic aqua complexes, trans(O,S)-[Ru(bpy)Cl(dmso-S) _2(OH_2)]X (1?X; X- = PF_6- or OTf-: CF_3SO_3~-) have been prepared by the treatment of cis(Cl),cis(S)-[Ru(bpy)Cl_2(dmso-S) _2] with Ag~+ in water at room temperature. When 1?X is dissolved in DMSO, MeOH, or MeCN, the OH_2 ligand in 1~+ is replaced with a solvent molecule (L) to yield trans(L,S)-[Ru(bpy)Cl(dmso-S) _2(L)]~+ (L = dmso-O, 2~+; L = MeOH, 3 ~+; and L = MeCN, 4~+), respectively. Moreover, 2?(OTf) is also obtained by the reaction of cis(Cl),cis(S)-[Ru(bpy)Cl _2(dmso-S)_2] with Ag(OTf) in DMSO on refluxing. The four kinds of crystal structures of trans(L,S)-[Ru(bpy)Cl(dmso-S)2(L)]PF_6 (1?PF_6?H_2O, 2?PF_6, 3?PF_6, and 4?PF_6?MeCN) revealed that the structural parameters, except for the sixth axial ligand, were essentially the same, and the four ligands, the bpy, two dmso-S, and the equatorial Cl- ligands are connected by hydrogen bonding. All the OH_2, dmso- O, MeOH, or MeCN ligands on the sixth coordination site at the axial position in cationic mono(bpy)ruthenium(II) complexes are labile so they are interconvertable. The [Ru(bpy)Cl(dmso-S)_2] unit does not change at room temperature even in solutions due to the presence of hydrogen networks among the bpy, two dmso-S, and the equatorial Cl- ligands.