Aggregation of Octahedral Thiolato Complexes by Forming Sulfur-Bridged Structures with Transition Metal Ions
Aggregation of Octahedral Thiolato Complexes by Forming Sulfur-Bridged Structures with Transition Metal Ions
复制标题
DOI：
10.1246/bcsj.77.627
复制
发表时间：
2004-04
影响因子：
4
通讯作者：
T. Konno
中科院分区：
文献类型：
--
作者：
T. Konno
本文综述了以2-氨基乙硫醇（aet）或L-半胱氨酸（L-cys）为配体的八面体金属配合物为基础的手性金属聚集体的合理构建及其作为供硫手性金属配体的功能研究进展。三硫羟合型fac（S）-[M（aet或L-cys-N，S）3或3-（M = Co III，Rh III，Ir III）]与过渡金属离子反应，生成了多种S-桥联的金属聚集体，其结构和手性性质与反应金属离子的性质密切相关。通过用其它过渡金属离子取代[Ni{Co（aet）2（en）} 2 ] 4 +中的Ni II离子，也实现了双硫醇合型cis（S）-[Co（aet）2（en）] 2 +的聚集.虽然这些三聚体的聚集（硫醇基）-和双（硫醇基）型八面体单元通常产生离散的S-桥连多核结构，一维和二维扩展聚合物结构，除了离散的三核结构，通过单体的反应，（硫醇）型[Co（aet或L-cys-N，S）-（en）2 ] 2 +或r +与银离子的配位，这是由于采用μ 3 -硫醇桥联方式和/或自由羧酸根的配位能力。
The main developments in rational construction of chiral metallo-aggregates based on octahedral metal complexes with 2-aminoethanethiolate (aet) or L-cysteinate (L-cys), as well as their functionality as an S-donating chiral metalloligand, are reviewed in this paper. The reactions of the tris(thiolato)-type fac(S)-[M(aet or L-cys-N,S) 3 or 3- (M = Co I I I , Rh I I I , Ir I I I ) with transition metal ions gave a variety of S-bridged metallo-aggregates, the structures and chiral properties of which are highly dependent on the nature of the reacting metal ions. The aggregation of the bis(thiolato)-type cis(S)-[Co(aet) 2 (en)] 2 + was also performed through the replacement of a Ni I I ion in [Ni{Co(aet) 2 (en)} 2 ] 4 + by other transition metal ions. While aggregation of these tris(thiolato)- and bis(thiolato)-types of octahedral units commonly produced discrete S-bridged polynuclear structures, one-dimensional and two-dimensional extended polymeric structures, besides a discrete trinuclear structure, were constructed by the reactions of the mono(thiolato)-type [Co(aet or L-cys-N,S)-(en) 2 ] 2 + o r + with silver ion, because of the adoption of μ 3 -thiolato bridging mode and/or the coordination ability of the free carboxylate group.