168294-12-0Relevant articles and documents
Partial halogenation of cyclic and branched perhydropentasilanes
Stueger, Harald,Mitterfellner, Thomas,Fischer, Roland,Walkner, Christoph,Patz, Matthias,Wieber, Stephan
, p. 6173 - 6179 (2012/07/14)
The perhydropentasilanes (H3Si)4Si and Si 5H10 were chlorinated with SnCl4 to give chlorohydropentasilanes without destruction of the Si-Si backbone. Tetrachloroneopentasilane (ClH2Si)4Si (2) was prepared in high yield from (H3Si)4Si and 3.5 equiv of SnCl 4, while Si5H10 and an equimolar amount of SnCl4 afforded a mixture of ～60% of ClSi5H9 (1) with polychlorinated cyclopentasilanes and unreacted starting material, which could not be separated by distillation. The selective monochlorination of Si5H10 was achieved starting from MesSi5Cl 9 (3; Mes = 2,4,6-trimethylphenyl) or TBDMP-Si5Cl 9 (4; TBDMP = 4-tert-butyl-2,6-dimethylphenyl). 3 or 4 was successfully hydrogenated with LiAlH4 to give MesSi5H 9 (6) or TBDMP-Si5H9 (7), which finally gave 1 along with aryl-H and Si5H10 after treatment with an excess of liquid anhydrous HCl. All compounds were characterized by standard spectroscopic techniques. For Si-H derivatives, the coupled 29Si NMR spectra were analyzed in detail to obtain an unequivocal structural assignment. The molecular structures of 2-4 were further confirmed by X-ray crystallography.
