Isolation of R6Si6 Dianion: A Bridged Tricyclic Isomer of Dianionic Hexasilabenzene
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 tricyclo...
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Published in | Journal of the American Chemical Society Vol. 140; no. 4; pp. 1219 - 1222 |
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Main Authors | , , , , |
Format | Journal Article |
Language | English |
Published |
WASHINGTON
American Chemical Society
31.01.2018
Amer Chemical Soc |
Subjects | |
Online Access | Get full text |
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Summary: | 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)]+ 2 counterions. 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. |
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Bibliography: | ObjectType-Article-1 SourceType-Scholarly Journals-1 ObjectType-Feature-2 content type line 23 |
ISSN: | 0002-7863 1520-5126 |
DOI: | 10.1021/jacs.7b12163 |