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- W2078762602 abstract "Dehalogenation of the organochlorosilanes Me3SiCl (I), Me2PrSiCl (II), Me3SiSiMe2Cl (III), Me3SiCH2SiMe2Cl (IV), ClCH2SiMe3 (V), ClCH2SiMe2SiMe3 (VI), ClCH2Me2SiSiMe2CH2Cl (VII), Me2SiCl2 (VIII), MePrSiCl2 (IX), Me3SiCH2SiMeCl2 (X), Me2SiCH2CH2SiMeCl2 (XI), Me3SiCH2CH2CH2SiMeCl2 (XII), ClCH2Si(H)MeCl (XIII), ClCH2SiM2Cl (XIV), ClMe2SiSiMe2Cl (XV), ClCH2CH2CH2Si(H)MeCl (XVI), ClCH2CH2CH2SiMe2Cl (XVII), ClCH2CH2OSiMe2Cl (XVIII), ClMe2SiCH2SiMe2Cl (XIX), ClMe2SiCH2CH2SiMe2Cl (XX), and ClMe2SiCH2CH2CH2SiMe2Cl (XXI) with K/Na alloy vapours at 0.1–1 Torr and 300–320°C yields products derived from the reactions of short-lived intermediates, such as silyl and silylmethyl radicals, silylenes, and sila-alkenes. In addition, small-ring silacycles of low stability are formed as the intermediates in some of the dehalogenation reactions. Combination and H-atom abstraction are the main reactions of silyl and silylmethyl radicals. These radicals are not prone to decomposition reactions when CH, CC, or SiC bonds are at the β-position to the radical centre. The pentamethyldisilanylmethyl radical decomposes at the β(SiSi) bond with the formation of Me2SiCH2 and the trimethylsilyl radical. The generation of alkylmethylsilylenes is accompanied by their decomposition, with the formation of 1-alkene and methylsilane. A mechanism has been proposed for the decomposition process, which involves intramolecular β (CH) insertion of alkylmethylsilylenes and [3 → 2 + 1]-thermocyclodecomposition of intermediate silacyclopropanes. The contribution of δ (CH) an ε(CH)insertion reactions is much less pronounced, and in the case of Me3Si(CH2)x,SiMe (x = 2 or 3), these insertion reactions result in the formation of five- or six-membered silacycles. We did not succeed in obtaining monosilacyclobutanes, as the intramolecular γ(CH)" @default.
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- W2078762602 date "1985-09-01" @default.
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- W2078762602 title "Silyl and silylmethyl radicals, silylenes, sila-alkenes, and small ring silacycles in reactions of organochlorosilanes with alkali metal vapours" @default.
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- W2078762602 doi "https://doi.org/10.1016/0022-328x(85)87334-4" @default.
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