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元素有机化学国家重点实验室

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【Chunming Cui's Group】Isolation of R6Si6 Dianion: A Bridged Tricyclic Isomer of Dianionic Hexasilabenzene

Release unit:SKLEOC   Release time:2018/01/17    Browse times:53

     


A new strategy for the highly selective synthesis of tricyclo[2,2,0,02,5]hexasilanes R6Si6X2 (R = 2,4,6-Me3C6H2; X = H, Cl) and a bridged tricyclic R6Si6 dianion starting from the tetrachlorotrisilane RCl2SiSi(H)RSiCl2R (1) was described. Reduction of 1 with lithium naphthalene afforded tricyclohexasilane R6Si6H2 (2), which was halogenated to give the dichloride R6Si6Cl2 (3). Reduction of 3 with four equivalents of potassium graphite in the presence of 18-crown-6 afforded the first R6Si6 dianion (5) paired with [K(18-crown-6)]+2counterions. The dianion 5 could act as a two-electron reductant toward transition metal halides and a nucleophile toward chlorosilanes. These reactions allowed the efficient and selective access to three types of silicon cages. The structures of the representative cages were confirmed by X-ray diffraction studies. Density functional theory calculations on 5 indicate that the negative charges are localized mainly on the anionic silicon atoms.

Read more:
Yang LiJianfeng Li Jianying ZhangHaibin Song, and Chunming Cui*. Isolation of R6Si6 Dianion: A Bridged Tricyclic Isomer of Dianionic Hexasilabenzene. J. Am. Chem. Soc., Article ASAP DOI: 10.1021/jacs.7b12163.
http://pubs.acs.org/doi/abs/10.1021%2Fjacs.7b12163.