- Selective synthesis of halosilanes from hydrosilanes and utilization for organic synthesis
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Selective synthesis of halosilanes has been examined. Various types of halosilanes and halohydrosilanes, such as R3SiX, R2SiHX, R2SiX2, RSiH2X, RSiHX2 (X=Cl, Br, F), were obtained by the reactions of the corresponding hydrosilanes with Cu(II)-based reagents selectively in high yields. This method could be also applied to the synthesis of chlorofluorosilanes and chlorohydrogermanes. On the other hand, iodo- and bromosilanes and germanes were obtained by Pd- or Ni-catalyzed hydride-halogen exchange reactions of hydrosilanes with alkyl or allyl halides. Their synthetic applications have been demonstrated by using iodo- and bromosilanes and chlorofluorosilanes.
- Kunai, Atsutaka,Ohshita, Joji
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- PdCl2 and NiCl2-catalyzed hydrogen-halogen exchange for the convenient preparation of bromo- and iodosilanes and germanes
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Bromination and iodination of hydrosilanes and germanes were studied. Treatment of hydrosilanes with an excess of ethyl, propyl, or allyl bromide in the presence of a catalytic amount of PdCl2 or NiCl2 gave bromosilanes in good to high yield by hydrogen-halogen exchange. By using methyl, propyl, or allyl iodide as the iodine source, similar iodination of hydrosilanes was readily performed. Halogenation of hydrogermanes also proceeded by similar treatment.
- Iwata, Arihiro,Toyoshima, Yutaka,Hayashida, Tsuyoshi,Ochi, Takahiko,Kunai, Atsutaka,Ohshita, Joji
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- The Mechanism of the Reaction of Molecular Bromine with Organosilicon Hydrides
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The kinetics of the bromination of 7 triarylsilanes and 14 other organosilicon hydrides by molecular bromine in CCl4 have been determined by the stopped flow method.For triethylsilane, Arrhenius parameters have been measured in octane and CCl4, and solvent effects determined in other solvents of different polarity.The results accord with a molecular mechanism involving one molecule of bromine and one of the organosilicon hydride, with partial positive charge build-up on silicon in the transition state.
- El-Durini, Nabil M. K.,Jackson, Richard A.
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p. 1275 - 1278
(2007/10/02)
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- The Influence of Substituents on the Nucleophilic Cleavage of the SiSi Linkage in Disilane Derivatives
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The rate constants of the SiSi cleavage with elementary bromine were measured in phenylmethyl- and pF-phenyl-methyldisilane derivatives.The influence of the substituents on the cleavage is discussed. - Keywords: Disilanederivatives; Rate constants, influence of substituents; SiSi-linkage
- Hengge, Edwin,Krysl, Franz Josef
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p. 731 - 742
(2007/10/02)
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