Department of Applied Chemistry, School of Engineering, The University of Tokyo, Tokyo, Japan.
Institute of Industrial Science, The University of Tokyo, 4-6-1 Meguro-ku, Komaba, Tokyo, Japan.
Chemistry. 2019 Mar 12;25(15):3761-3765. doi: 10.1002/chem.201805678. Epub 2019 Feb 14.
The construction of well-defined transition-metal clusters has attracted substantial attention due to their unique chemical and/or physical properties. Metal clusters with 1D or 2D structures are now accessible by template-synthesis methods, in which multiple metal atoms are arranged with the aid of template molecules and their 1D or 2D structures. However, the rational synthesis of 3D clusters remains challenging, mostly due to a lack of appropriate template molecules. Herein, we report the rational synthesis of a 2D butterfly shaped Pd framework (2) and 3D edge-sharing Pd tetrahedra (5) by treatment of easily available organosilicon compounds with Pd(CNtBu) . The diphenylsilylene moiety thereby serves as the key component to generate the butterfly structure of the Pd clusters in 2. A dimensionality expansion, induced by two Cl atoms, of two butterfly shaped Pd subunits supported by two diphenylsilylene moieties afforded the edge-sharing tetrahedral architecture of the Pd cluster in 5.
由于具有独特的化学和/或物理性质，结构明确的过渡金属簇的构建引起了人们的极大关注。现在可以通过模板合成方法获得具有 1D 或 2D 结构的金属簇，其中多个金属原子在模板分子的辅助下排列成 1D 或 2D 结构。然而，由于缺乏合适的模板分子，合理合成 3D 簇仍然具有挑战性。在此，我们报告了通过用 Pd(CNtBu)处理易得的有机硅化合物，合理合成了二维蝴蝶形 Pd 骨架（2）和 3D 共用边的 Pd 四面体（5）。二苯硅烯部分因此成为在 2 中生成 Pd 簇的蝴蝶结构的关键组成部分。由两个 Cl 原子诱导的二维蝴蝶形 Pd 亚基的维度扩展，由两个二苯硅烯部分支撑，得到 Pd 簇的共用边四面体结构在 5 中。
