A Remarkable Metal-Crossing between Thiolato-Bridged Tetragold(I) and Tetrasilver(I) Metallorings
A Remarkable Metal-Crossing between Thiolato-Bridged Tetragold(I) and Tetrasilver(I) Metallorings
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硫奥拉托桥四金 (I) 和四银 (I) 金属之间的显着金属交叉
DOI：
10.1002/asia.201100668
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发表时间：
2011
期刊：
影响因子：
--
通讯作者：
瀧野祐輔
中科院分区：
文献类型：
--
作者：
今野巧;瀧野祐輔
含金属的金属环的设计和合成是配位化学和超分子化学领域的一个活跃的研究领域，因为它们具有美丽的结构和有趣的性质。[1]产生这种分子的常用方法是通过自组装过程将刚性有机配体与过渡金属离子/络合物以封闭形式连接;迄今为止，已经使用这种方法制备了大量具有MSNN、MSNO、MSNP和MSNS配位键的分子环。[2-4]这种方法有利于构建由金属配体重复单元组成的均聚环结构，表示为[ML] n，其环尺寸可以通过单元的数量和长度来控制。[3]相比之下，通过使用单一种类的配体与不同种类的金属离子的组合的简单自组装方法来制备其中两种或更多种不同的金属离子精确定位的异金属分子环并不简单。到目前为止，文献中只出现了相对少量的杂金属分子环，[4，5]因此，发现一种允许以合理的方式选择性形成杂金属分子环的方法是该研究领域的关键问题。作为我们在开发衍生自含硫醇配体的金属配合物系统方面正在进行的努力的一部分，[6]本文中，我们报告了硫醇桥连的四金（I）和四银（I）配合物的合成和表征，其中四个金（I）或银（I）离子被四个亚氨基硫醇盐以方环形式桥连（方案1）。值得注意的是，发现四金（I）和四银（I）分子环的简单混合可以快速且唯一地得到异金属分子环，其中两个金（I）和两个银（I）离子通过四个亚氨基硫醇盐以类似的环形式交替桥接。虽然[M（SR）] n型的硫醇桥连金属环结构对于M=银（I）和金（I）是众所周知的;[7]这是首次观察到通过金（I）和银（I）同环之间的金属交叉反应区域选择性地形成异金属分子环。2-（4-二甲氨基苯基）苯并噻唑啉与氯代（四氢噻吩）金（I）在三乙胺存在下在氯仿中反应，得到黄色溶液，从中分离出黄色粉末（1）。用高氯酸银（I）代替氯代（四氢噻吩）金（I）进行类似的反应也得到黄色粉末（2）。的
The design and synthesis of metal-containing molecular rings of polygon-type has been an active area of research in the field of coordination chemistry and supramolecular chemistry because of their architectural beauty and often their intriguing properties.[1] The common approach to create such molecules is the linkage of rigid organic ligands with transition metal ions/complexes in a closed form through self-assembly processes; a large number of molecular rings with MÀN, MÀO, MÀP, and MÀS coordination bonds have been prepared so far using this approach.[2–4] This approach is beneficial for the construction of homometallic ring structures consisting of metal–ligand repeating units, denoted as [ML] n, the ring-size of which can be controlled by the number and length of the units.[3] In contrast, it is not straightforward to prepare heterometallic molecular rings, in which two or more different metal ions are precisely positioned, by a simple self-assembly approach using a combination of a single kind of ligand with different kinds of metal ions. To date, only a relatively small number of heterometallic molecular rings has appeared in the literature,[4, 5] and thus, the finding of a methodology that allows the selective formation of heterometallic molecular rings in a rational manner is a key concern in this research area. As part of our ongoing efforts in the development of metalloring systems derived from thiol-containing ligands,[6] herein we report the synthesis and characterization of thiolatobridged tetragold (I) and tetrasilver (I) complexes, in which four gold (I) or silver (I) ions are bridged by four iminothiolates in a square-ring form (Scheme 1). Remarkably, simple mixing of the tetragold (I) and tetrasilver (I) molecular rings was found to quickly and exclusively give a heterometallic molecular ring, in which two gold (I) and two silver (I) ions are alternately bridged by four iminothiolates in an analogous ring form. Whilst thiolato-bridged metalloring structures of [M (SR)] n type are well-known for M= silver (I) and gold (I);[7] this is the first observation of a regioselective formation of a heterometallic molecular ring by the metalcrossing reaction between gold (I) and silver (I) homometallic rings.The 1: 1 reaction of 2-(4-dimethylaminophenyl) benzothiazoline with chloro (tetrahydrothiophene) gold (I) in the presence of triethylamine in chloroform afforded a yellow solution, from which a yellow powder (1) was isolated. A similar reaction using silver (I) perchlorate instead of chloro (tetrahydrothiophene) gold (I) also gave a yellow powder (2). The