Halogen-Exchange Reactions of Iminophosphonamido-Chlorosilylenes with Alkali Halides: Convenient Synthesis of Heavier Halosilylenes
Halogen-Exchange Reactions of Iminophosphonamido-Chlorosilylenes with Alkali Halides: Convenient Synthesis of Heavier Halosilylenes
复制标题
亚氨基膦酰氨基-氯代甲硅烷基与碱金属卤化物的卤素交换反应：方便合成较重的卤代甲硅烷基
DOI：
10.1021/acs.inorgchem.1c03869
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发表时间：
2022
影响因子：
4.6
通讯作者：
Nakata Norio
中科院分区：
文献类型：
--
作者：
Takahashi Shintaro;Sekiguchi Jueri;Nakaya Kazuki;Ishii Akihiko;Nakata Norio
卤素取代硅烯是合成硅基低价和多键化合物的重要组成部分。然而，关于含有溴和碘的较重的卤代硅烯的报告数量仍然有限。在这里，我们提出了一种由亚磷酰胺配体支撑的溴和碘硅烯的简便合成方法。在四氢呋喃中，氯硅氧烷与碱卤化物进行卤素交换反应，成功合成了较重的卤代硅氧烷[Ph2P(thbun)2] 6 （2: X = Br,3: X = I）。作为2和3的反应活性的证明，2和3在c6d6中与元素硒的氧化加成反应产生相应的无色晶体溴-(5)或碘硅-硒酮(6)。2、3、5和6的分子结构通过光谱手段和单晶x射线衍射分析得到了完整的表征。此外，利用密度泛函理论（DFT）计算研究了卤素原子对卤代硅酮1 - 3和卤代硅酮4 - 6电子态的影响。
Halogen-substituted silylenes are an important building block for synthesizing silicon-based low-valent and multiple-bond species. However, the number of reports on heavier halosilylenes that contain bromine and iodine is still limited. Here, we present a convenient synthesis for bromo- and iodosilylenes supported by an iminophosphonamide ligand. The heavier halosilylenes [Ph2P(tBuN)2]SiX (2: X = Br,3: X = I) were successfully synthesized via the halogen-exchange reaction of chlorosilylene1with alkali halides in THF. As a demonstration of the reactivity of2and3, oxidative addition reactions of2and3with elemental selenium in C6D6afforded the corresponding bromo- (5) or iodosilylene-selone (6) as colorless crystals. The molecular structures of2,3,5, and6were fully characterized by spectroscopic means and single-crystal X-ray diffraction analysis. Furthermore, the effects of the halogen atom on the electronic state of halosilylenes1–3and halosilylene–selones4–6were investigated using density functional theory (DFT) calculations.