Tamura Motoshi, Matsuura Noriyuki, Kawamoto Tatsuya, Konno Takumi
Department of Chemistry, Graduate School of Science, Osaka University, Toyonaka, Osaka 560-0043, Japan.
Inorg Chem. 2007 Aug 20;46(17):6834-6. doi: 10.1021/ic700572r. Epub 2007 Jul 17.
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 RuIIAgIRuII trinuclear complex, [Ag{Ru(aet)(bpy)2}2]3+, in which two [RuII(aet)(bpy)2]+ units are linked by an AgI atom. When this complex was treated with HCl in acetonitrile/water, a disulfide-bridged RuIIRuII dinuclear complex, [Ru2(cysta)(bpy)4]4+ (cysta = cystamine), was produced as a result of the removal of an AgI 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.
在乙醇/水体系中，[Ru(solvent)2(bpy)2]2+（bpy = 2,2'-联吡啶）与硫乙醇胺（Haet，2-氨基乙硫醇）在Ag+存在下反应，生成了一个硫醇盐桥联的RuIIAgIRuII三核配合物[Ag{Ru(aet)(bpy)2}2]3+，其中两个[RuII(aet)(bpy)2]+单元通过一个AgI原子相连。当该配合物在乙腈/水体系中用HCl处理时，由于AgI原子的去除和硫醇盐基团的自氧化，生成了一个二硫键桥联的RuIIRuII双核配合物[Ru2(cysta)(bpy)4]4+（cysta = 胱胺）。研究发现，通过锌还原辅助的Ag+处理，[Ru2(cysta)(bpy)4]4+中的双核结构可恢复为[Ag{Ru(aet)(bpy)2}2]3+。
