Tian Miao, Zhang Jianying, Yang Hao, Cui Chunming
State Key Laboratory of Elemento-Organic Chemistry and College of Chemistry, Nankai University, Tianjin 300071, People's Republic of China.
J Am Chem Soc. 2020 Mar 4;142(9):4131-4135. doi: 10.1021/jacs.0c00519. Epub 2020 Feb 20.
Herein we report the first synthesis of a 1-magnesium-2,3-disilacyclopropene and a related bis(disilenide). Reduction of (boryl)tribromosilane (, boryl = (HCArN)B, Ar = 2,6-PrCH) with magnesium in THF afforded boryl-substituted magnesium complex [(boryl)Si]Mg(THF) () in good yield, whereas reduction of (boryl)trichlorosilane () with KC in THF led to the isolation of bridged alkoxy alkyl bis(disilenide) (THF)K(boryl)Si═Si(boryl)O(CH)(boryl)Si═Si(boryl)K(THF) () via ring opening of a THF molecule. X-ray diffraction analysis of confirmed the presence of the novel SiMg three-membered ring as well as the Si═Si double bond, which existed in a noticeably twisted B-Si-Si-B array. Complex also represents the first reported example of a stable disilyne dianion.
在此，我们报道了1-镁-2,3-二硅环丙烯和一种相关双（二硅烯基）的首次合成。在四氢呋喃中用镁还原（硼基）三溴硅烷（硼基 = (HCArN)B，Ar = 2,6-PrCH），以良好的产率得到硼基取代的镁配合物[(硼基)Si]Mg(THF)（），而在四氢呋喃中用KC还原（硼基）三氯硅烷（），通过四氢呋喃分子的开环导致分离出桥连烷氧基烷基双（二硅烯基）(THF)K(硼基)Si═Si(硼基)O(CH)(硼基)Si═Si(硼基)K(THF)（）。对的X射线衍射分析证实了新型SiMg三元环以及Si═Si双键的存在，它们存在于明显扭曲的B-Si-Si-B排列中。配合物也是首次报道的稳定二硅炔二价阴离子的例子。
