Dicationic 1-Germa and 1-Stannavinylidenes: Synthesis, Structure, and Reactivity.

IF 8.5 Q1 CHEMISTRY, MULTIDISCIPLINARY

JACS Au Pub Date : 2025-02-19 eCollection Date: 2025-03-24 DOI:10.1021/jacsau.4c01139

Yuankai Li, Huan Mu, Zhuchunguang Liu, Zexin Qi, Jiliang Zhou, Zhaowen Dong

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Abstract

The synthesis of heteronuclear vinylidene analogues containing heavier group 14 elements (R₂C=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 (3Ge) and 1-stannavinylidene (3Sn) by using sym-bis(2-pyridyl)-tetraphenylcarbodiphosphorane (CDPPy₂) as a donor ligand. Both 3Ge and 3Sn 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 3Ge and 3Sn 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 3Ge with IDippMCl (M = Cu, Ag, Au) give the M-Cl bond addition products. Mechanistic studies on the activation of the Au-Cl bond by 3Ge 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.

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由于含有较重的第 14 族元素（R2C=E:，E = Si、Ge、Sn）的异核亚乙烯基类似物固有的不稳定性，其合成一直是一项具有挑战性的任务。在本研究中，我们报告了以双(2-吡啶基)-四苯基碳二膦（CDPPy2）为供体配体合成二阳离子 1-锗亚氨基（3Ge）和 1-锡亚氨基（3Sn）的情况。3Ge 和 3Sn 均已通过单晶 X 射线衍射分析、核磁共振光谱分析和高分辨率质谱分析进行了表征。在理论计算结果的支持下，结构分析证实 3Ge 和 3Sn 具有极化 C=E 双键和位于 E 原子（E = Ge 和 Sn）的孤电子对。3Ge 与 IDippMCl（M = Cu、Ag、Au）反应生成 M-Cl 键加成产物。对 3Ge 活化 Au-Cl 键的机理研究证明了它的亲和性。这项工作是利用骨架配体作为σ和π供体合成较重的异核乙烯基类似物的一个实例。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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