Crystal Structures and Substitution Reactions of trans(O,S)-[Ru(bpy)Cl(dmso-S)2(OH2)]+ 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)

• Published in: Bulletin of the Chemical Society of Japan 2010-12, Vol.83 (12), p.1518-1527
• Main Authors: Toyama, Mari, Iwamatsu, Shinobu, Inoue, Ken-ichi, Nagao, Noriharu
• Format: Article
• Language: English
• ISSN: 0009-2673; 1348-0634
• DOI: 10.1246/bcsj.20100224

The labile cationic aqua complexes, trans(O,S)-[Ru(bpy)Cl(dmso-S)2(OH2)]X (1·X; X− = PF6− or OTf−: CF3SO3−) have been prepared by the treatment of cis(Cl),cis(S)-[Ru(bpy)Cl2(dmso-S)2] with Ag+ in water at room temperature. When 1·X is dissolved in DMSO, MeOH, or MeCN, the OH2 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)Cl2(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)]PF6 (1·PF6·H2O, 2·PF6, 3·PF6, and 4·PF6·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 OH2, 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.