Rational creation of chiral multinuclear and metallosupramolecular compounds from thiol-containing amino acids
Rational creation of chiral multinuclear and metallosupramolecular compounds from thiol-containing amino acids
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DOI：
10.1039/c0dt01660h
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发表时间：
2011-07-28
影响因子：
4
通讯作者：
Konno, Takumi
中科院分区：
文献类型：
--
作者：
Igashira-Kamiyama, Asako;Konno, Takumi
本论文的主要内容是基于青霉胺（pen）的线性金属配合物，在手性多核和金属超分子化合物的合理构建及其作为多齿手性金属配体的功能方面的研究进展。单核Au I配合物[Au（D-pen）（2）]（3-）（其中两个D-pen配体通过硫原子与Au I中心结合）与过渡金属离子反应，得到了多种S-桥连的杂环多核配合物，其结构和性质高度依赖于反应金属离子的性质。所产生的多核配合物仍然充当金属配体，当它们具有游离胺和/或羧酸根基团时，通过与第三金属离子反应导致形成异三金属超分子结构。虽然[Au（D-pen）2]（3-）中的Au S键通常在与金属离子的反应过程中保留，但相应的Hg-II络合物[Hg（D-pen）2]（2-）中的Hg-S键并非如此。此外，还发现[Au（L-cys）（2）]（3-）（cys =半胱氨酸）的多核配合物具有与[Au（L-pen）（2）]（3-）相反的手性行为。
Developments in the rational creation of chiral multinuclear and metallosupramolecular compounds based on linear-type metal complexes with penicillaminate (pen), as well as their functionality as a multidentate chiral metalloligand, is the main subject of this paper. The reactions of a mononuclear Au-I complex, [Au(D-pen)(2)](3-), in which two D-pen ligands bind to an AuI center through thiolato S atoms, with transition metal ions afford a variety of S-bridged heterobimetallic multinuclear complexes, the structures and properties of which are highly dependent on the nature of reacting metal ions. The created multinuclear complexes still act as a metalloligand when they possess free amine and/or carboxylate groups, leading to the formation of heterotrimetallic supramolecular structures by reacting with third metal ions. While the Au S bonds in [Au(D-pen)2](3-) are generally retained in the course of the reactions with metal ions, this is not the case for the Hg-S bonds in the corresponding Hg-II complex, [Hg(D-pen)2](2-). A remarkable chiral behavior of multinuclear complexes composed of [Au(L-cys)(2)](3-) (cys = cysteinate), which is opposite to that composed of [Au(L-pen)(2)](3-), is also presented.