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由双(联吡啶)钌(II)单元与螯合的2-氨基乙硫醇盐组成的硫醇盐桥联RuIIAgIRuII三核配合物:转化为二硫键桥联的RuIIRuII双核配合物。

Thiolato-bridged RuIIAgIRuII trinuclear complex composed of bis(bipyridine)ruthenium(II) units with chelating 2-aminoethanethiolate: conversion to a disulfide-bridged RuIIRuII dinuclear complex.

作者信息

Tamura Motoshi, Matsuura Noriyuki, Kawamoto Tatsuya, Konno Takumi

机构信息

Department of Chemistry, Graduate School of Science, Osaka University, Toyonaka, Osaka 560-0043, Japan.

出版信息

Inorg Chem. 2007 Aug 20;46(17):6834-6. doi: 10.1021/ic700572r. Epub 2007 Jul 17.

Abstract

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.

摘要

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+。

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