18038-55-6Relevant articles and documents
Exhaustively Trichlorosilylated C1 and C2 Building Blocks: Beyond the Müller-Rochow Direct Process
Georg, Isabelle,Teichmann, Julian,Bursch, Markus,Tillmann, Jan,Endeward, Burkhard,Bolte, Michael,Lerner, Hans-Wolfram,Grimme, Stefan,Wagner, Matthias
supporting information, p. 9696 - 9708 (2018/07/21)
The Cl--induced heterolysis of the Si-Si bond in Si2Cl6 generates an [SiCl3]- ion as reactive intermediate. When carried out in the presence of CCl4 or Cl2C=CCl2 (CH2Cl2 solutions, room temperature or below), the reaction furnishes the monocarbanion [C(SiCl3)3]- ([A]- 92%) or the vicinal dianion [(Cl3Si)2C-C(SiCl3)2]2- ([B]2- 85%) in excellent yields. Starting from [B]2-, the tetrasilylethane (Cl3Si)2(H)C-C(H)(SiCl3)2 (H2B) and the tetrasilylethene (Cl3Si)2C=C(SiCl3)2 (B; 96%) are readily available through protonation (CF3SO3H) or oxidation (CuCl2), respectively. Equimolar mixtures of H2B/[B]2- or B/[B]2- quantitatively produce 2 equiv of the monoanion [HB]- or the blue radical anion [B?]-, respectively. Treatment of B with Cl- ions in the presence of CuCl2 furnishes the disilylethyne Cl3SiC≡CSiCl3 (C; 80%); in the presence of [HMe3N]Cl, the trisilylethene (Cl3Si)2C=C(H)SiCl3 (D; 72%) is obtained. Alkyne C undergoes a [4+2]-cycloaddition reaction with 2,3-dimethyl-1,3-butadiene (CH2Cl2, 50 °C, 3d) and thus provides access to 1,2-bis(trichlorosilyl)-4,5-dimethylbenzene (E1; 80%) after oxidation with DDQ. The corresponding 1,2-bis(trichlorosilyl)-3,4,5,6-tetraphenylbenzene (E2; 83%) was prepared from C and 2,3,4,5-tetraphenyl-2,4-cyclopentadien-1-one under CO extrusion at elevated temperatures (CH2Cl2, 180 °C, 4 d). All closed-shell products were characterized by 1H, 13C{1H}, and 29Si NMR spectroscopy; an EPR spectrum of [nBu4N][B?] was recorded. The molecular structures of [nBu4N][A], [nBu4N]2[B], B, E1, and E2 were further confirmed by single-crystal X-ray diffraction. On the basis of detailed experimental investigations, augmented by quantum-chemical calculations, plausible reaction mechanisms for the formation of [A]-, [B]2-, C, and D are postulated.
Gas-phase reactions of hexachlorodisilane with chloroform, carbon tetrachloride, and Di- and tetrachloroethylenes
Chernyshev,Komalenkova,Kapitova,Bykovchenko
, p. 1113 - 1116 (2007/10/03)
Gas-phase reactions of hexachlorodisilane with chloroalkanes (CHCl3 and CCl4) and chloroalkenes (ClCH=CHCl and Cl2C=CCl2) are studied. Dichlorosilylenes generated from Si2Cl6 insert into the C-Cl bonds in chloroalkanes; with chloroalkenes, insertion into the C-Cl bonds occurs along with cyclo-addition to the C=C bonds.
Synthesis and Spectroscopic Characterization of Di- and Trisilylethenes
Schmidbaur, H.,Ebenhoech, J.
, p. 1543 - 1548 (2007/10/02)
Di- and trisilylethenes have been prepared by catalytic hydrosilylation of trimethylsilyl-, bis(trimethylsilyl)- and bis(trichlorosilyl)ethyne and converted into the hydrogenated derivatives by LiAlH4-reduction.The stereochemistry of the products and the effects of substitution of methyl vs. chlorine ligands on the NMR coupling constants J(29Si/1H) have been investigated by analysis of selectively (Me)-decoupled 29Si NMR spectra.From the results it has been concluded, that the catalytic hydrosilylation of silylated ethynes proceeds in a stereospecific syn fashion yield ing trans adducts.Substitution of methyl by chlorine at one or two Si-atoms in tris(trimethylsilyl)ethene leads to an increase of the coupling constant J(29Si/1H vinyl) with the chlorinated Si-atoms and reduces the values for those Si-atoms, where the methyl groups are retained. - Keywords: Di- and Trisilylethenes, Catalytic Hydrosilylation
