One-Electron-Mediated Rearrangements of 2,3-Disiladicarbene

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• 作者：Kartik Chandra Mondal ; Prinson P. Samuel ; Herbert W. Roesky ; Rinat R. Aysin ; Larissa A. Leites ; Sven Neudeck ; Jens L眉bben ; Birger Dittrich ; Nicole Holzmann ; Markus Hermann ; Gernot Frenking
• 刊名：Journal of the American Chemical Society
• 出版年：2014
• 出版时间：June 25, 2014
• 年：2014
• 卷：136
• 期：25
• 页码：8919-8922
• 全文大小：301K
• ISSN：1520-5126

文摘

A disiladicarbene, (Cy-cAAC)₂Si₂ (2), was synthesized by reduction of Cy-cAAC:SiCl₄ adduct with KC₈. The dark-colored compound 2 is stable at room temperature for a year under an inert atmosphere. Moreover, it is stable up to 190 掳C and also can be characterized by electron ionization mass spectrometry. Theoretical and Raman studies reveal the existence of a Si鈺怱i double bond with a partial double bond between each carbene carbon atom and silicon atom. Cyclic voltammetry suggests that 2 can quasi-reversibly accept an electron to produce a very reactive radical anion, 2^{鈥⑩€?/b>}, as an intermediate species. Thus, reduction of 2 with potassium metal at room temperature led to the isolation of an isomeric neutral rearranged product and an anionic dimer of a potassium salt via the formation of 2^{鈥⑩€?/b>}.