Li Yuankai, Mu Huan, Liu Zhuchunguang, Qi Zexin, Zhou Jiliang, Dong Zhaowen
Key Laboratory of Green Chemistry & Technology, Ministry of Education, College of Chemistry, Sichuan University, Chengdu 610064, P. R. China.
JACS Au. 2025 Feb 19;5(3):1289-1298. doi: 10.1021/jacsau.4c01139. eCollection 2025 Mar 24.
The synthesis of heteronuclear vinylidene analogues containing heavier group 14 elements (RC=E:, E = Si, Ge, Sn) has been a challenging task due to their inherent instability. In this study, we report the synthesis of dicationic 1-germavinylidene () and 1-stannavinylidene () by using sym-bis(2-pyridyl)-tetraphenylcarbodiphosphorane (CDPPy) as a donor ligand. Both and have been characterized by single-crystal X-ray diffraction analysis, NMR spectroscopy, and high-resolution mass spectrometry. The structural analysis, supported by the results of theoretical calculations, confirms that and feature a polarized C=E double bond and a lone pair of electrons located at the E atom (E = Ge and Sn). The reactions of with IDippMCl (M = Cu, Ag, Au) give the M-Cl bond addition products. Mechanistic studies on the activation of the Au-Cl bond by demonstrate its ambiphilicity. This work represents an example of the utilization of a carbone ligand as both an σ and π donor for the synthesis of heavier heteronuclear vinylidene analogues.
由于其固有的不稳定性，合成含有较重第14族元素的异核亚乙烯基类似物（RC=E:，E = Si、Ge、Sn）一直是一项具有挑战性的任务。在本研究中，我们报告了通过使用对称双（2-吡啶基）-四苯基碳二磷烷（CDPPy）作为供体配体来合成双阳离子1-锗亚乙烯基（）和1-锡亚乙烯基（）。和均已通过单晶X射线衍射分析、核磁共振光谱和高分辨率质谱进行了表征。在理论计算结果的支持下，结构分析证实和具有极化的C=E双键以及位于E原子（E = Ge和Sn）上的一对孤对电子。与IDippMCl（M = Cu、Ag、Au）的反应生成M-Cl键加成产物。对通过活化Au-Cl键的机理研究证明了其双亲性。这项工作代表了利用碳配体作为σ和π供体来合成较重异核亚乙烯基类似物的一个例子。
