Abstract
The previously unknown disilanes 1,1,2-trichlorotri(1-naphthyl)disilane and 1,2-dichlorotetra(1-naphthyl)disilane were prepared by the reaction of 1-lithionaphthalenide with hexachlorodisilane. Reduction with LiAlH4 afforded 1,1,2-tri(1-naphthyl)disilane. Treatment of 1,2-di(1-naphthyl)disilane and 1,1,2-tri(1-naphthyl)disilane with liquid hydrogen chloride gave ClH2SiSiH2Cl and ClH2SiSiHCl2 in quantitative yields, along with naphthalene. The chlorodisilanes were easily separated and purified by fractional condensation. Both disilanes are stable for weeks at room temperature, but undergo rapid H/Cl exchange reactions and SiSi cleavage upon the addition of traces of catalysts such as AlCl3. The 29Si chemical shifts and J(29Si,1H) coupling constants, including those of ClH2SiSiH3 and Cl2HSiSiH3, are reported. The infrared and Raman vibrational spectra clearly prove that both chlorodisilanes comprise mixtures of gauche and anti rotamers in the liquid state.
Published Version
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