The reaction of [Ru(solvent)(2)(bpy)(2)](2+) (bpy = 2,2'-bipyridine) with Haet (2-aminoethanethiol) in ethanol/water in the presence of Ag+ gave a thiolato-bridged (RuAgRuII)-Ag-II-Ru-I trinuclear complex, [Ag{Ru(aet)(bpy)(2)](2)](3+), in which two [Ru-II(aet)(bpy)2](+) units are linked by an Ag-I atom. When this complex was treated with HCl in acetonitrile/water, a disulfide-bridged (RuRuII)-Ru-II dinuclear complex [RU2(cysta)(bpy)(4)](4+) (cysta = cystamine), was produced as a result of the removal of an Ag-I atom and the autoxidation of thiolato groups. It was found that the dinuclear structure in [RU2(cysta)(bpy)4]4+ is reverted back to [Ag{Ru(aet)(bpy)(2)}(2)](3+) by treatment with Ag+ assisted by Zn reduction.