Karlsruhe Institute of Technology (KIT), Institute of Nanotechnology, P.O. Box 3640, 76021, Karlsruhe, Germany.
Angew Chem Int Ed Engl. 2023 Jun 5;62(23):e202303037. doi: 10.1002/anie.202303037. Epub 2023 May 3.
Pseudo-tetrahedral units of p-block atoms proved to be excellent building blocks for novel molecular architectures and for introducing new elemental combinations which are not otherwise accessible. In this work, we present a series of clusters obtained by reactions of binary Ge/As anions with [MPh ] (M=Zn, Cd, Hg; Ph=phenyl). The study is grounded on the fact that the binary reactant gained by extracting the solid 'K GeAs' with ethane-1,2-diamine (en) co-exists as (Ge As ) and (Ge As) in solution. This allows for a larger variety of products by 'selecting' the most suitable species for the final ternary complex to crystallize. The reactions afforded the unprecedented first step of the corresponding interaction, thus attachment of (MPh) to a pseudo-tetrahedral unit in [PhZn(Ge As)] (1) and [PhHg(Ge As)] (2), and complex anions with two, three, or four units, [(Ge As)Zn(Ge As )] (3), [Cd (Ge As) ] (4), and [Zn (Ge As) ] (5). Quantum chemistry confirmed the compositions and the positions of the Ge or As atoms, beside explaining structural peculiarities. The subtle impact of different [MR ] reactants was additionally studied by corresponding reactions using [ZnMes ] (Mes=mesityl), which showed success in selectively crystallizing [MesZn(Ge As)] (6). Based on our findings, we derive a suggestion of the underlying reaction cascade.
p 区原子的拟四面体单元被证明是构建新型分子架构和引入新元素组合的极好构建块，这些新元素组合在其他情况下无法获得。在这项工作中，我们通过二元 Ge/As 阴离子与 [MPh ]（M=Zn、Cd、Hg；Ph=phenyl）的反应得到了一系列团簇。研究的基础是，通过用乙烷-1,2-二胺（en）提取固体'K GeAs'获得的二元反应物在溶液中以 (Ge As ) 和 (Ge As) 的形式共存。这允许通过“选择”最适合最终三元配合物结晶的最合适物种来获得更多种类的产物。反应提供了相应相互作用的前所未有的第一步，从而将 (MPh) 附着到 [PhZn(Ge As)]（1）和 [PhHg(Ge As)]（2）中的拟四面体单元上，以及具有两个、三个或四个单元的络阴离子，[(Ge As)Zn(Ge As )]（3）、[Cd (Ge As) ]（4）和 [Zn (Ge As) ]（5）。量子化学证实了组成和 Ge 或 As 原子的位置，并解释了结构特性。通过使用 [ZnMes ]（Mes=mesityl）进行相应的反应，进一步研究了不同 [MR ] 反应物的细微影响，该反应成功地选择性地结晶了 [MesZn(Ge As)]（6）。基于我们的发现，我们提出了一个潜在反应级联的建议。
