Bildung siliciumorganischer Verbindungen. 110. Reaktionen von (Cl3Si)2CCl2, seiner Si-methylierten Derivate,von (Cl3Si)2CHCl, (Cl3Si)2C(Cl)Me und Me2CCl2 mit Silicium (Cu-Kat.)

Formation of Organosilicon Compounds. 110. Reactions of (Cl₃Si)₂CCl₂ and its Si-methylated Derivatives as well as of (Cl₃Si)₂CHCl, (Cl₃Si)₂C(Cl)Me and Me₂CCl₂ with Silicon (Cu cat.) The reactions of (Cl₃Si)₂CCl₂ 1 , its Si-methylated derivatives (Me₃Si)₂CCl₂ 8 , Me₃Si? CCl₂? SiMe₂Cl 9 , (ClMe₂Si)₂CCl₂ 10 , Me₃Si? CCl₂? SiMeCl₂ 11 , Cl₂MeSi? CCl₂? SiCl₃ 12 as well as of (Cl₃Si)₂CHCl 38 , (Cl₃Si)₂CClMe 39 and of Me₂CCl₂ with Si (Cu cat.) in a fluid bed reactor ( 38 and 39 also in a stirred solid bedreactor) arc presented. While (Cl₃Si)₂CCl₂ 1 yields C(SiCl₃)₄ 2 the 1,1,3,3-tetrachloro-2,2,4,4-tetrakis(trichlorsilyl)-1,3-disilacyclobutane Si₆C₂Cl₁₆ 3 and the related C-spiro linked disilacyclobutanes Si₈C₃Cl₂₀ 4 , Si₁₀C₄Cl₂₄ 5 , Si₁₂C₅Cl₂₈ 6 , Si₁₄C₆Cl₃₂ 7 this type of compounds is not obtained starting from the Si-methylated derivatives 8, 9, 10, 11 They Produce a number of variously Si-chlorinated and -methylated tetrasila- and trisilamethanes. However, Cl₂MeSi? CCl₂? SiCl₃ 12 forms besides of Si-chlorinated trisilamethanes also the disilacyclobutanes Si₆C₂Cl₁₅Me 34 and cis- and trans Si₆C₂Cl₁₄Me₂ 35 as well as the spiro-linked disilacyclobutanes Si₈C₃Cl₁₉Me 36 , Si₈C₃Cl₁₈Me₂ 37 . (Cl₃Si)₂CHCl 38 mainly yields HC(SiCl₃)₃ 31 and also the disilacyclobutanes cis- and trans-(Cl₃Si)HC(SiCl₂)₂CH(SiCl₃) 41 and (Cl₃Si)₂C(SiCl₂)₂CH(SiCl₃) 45 the 1,3,5-trisilacyclohexane Cl₃Si(H)C? SiCl₂]₃ 44 as well as (Cl₃Si)₂CH]₂SiCl₂, and (Cl₃Si)₂CClMe 39 mainly yields (Cl₃Si)₂C?CH₂and (Cl₃Si)₂besides of HC(SiCl₃)₃, MeC(SiCl₃)₃and (Cl₃Si)₃C? SiCl₂Me.,. Me₂CCl₂ 59 mainly yields Me(Cl)C?CH₂, Me₂CHCl and HCl₂Si? CMe₂? SiCl₃, besides of Me₂C(SiCl₃)₂ and Me₂C(SiCl₂H)₂ Compound 3 crystallizes triclinically in the space group P1 (Nr. 2) mit a = 900,3, b = 914,0, c = 855,3 pm, α = 116,45°, β = 101,44°, γ = 95,86° and one molecule per unit cell. Compound 4 crystallizes monoclinically in thc space group C2/c (no. 15) with a = 3158.3,b = I 103.7, c = 2037.4 pm, β = 1 16.62° and 8 molecules pcr unit cell. The disilacyclobutane ring of compound 3 is plane, showing a mean distance of d (Si-C) =19 1.8 pm and the usual deformations of endocyclic angles: α_Si = 94,2°> 85,8° = α_C.The spiro-linked disilacyclobutane rings of compound 4 are slightly folded by a mean angle of (19.0°). Their mean distances were found to be d (Si? C) = 190.4 pm relating to the central carbon atom and 192.0 pm to the outer ones, respectively. The deformations of endocyclic angles: α_Si = 93,9°> 84,4° = α_C are comparable to those of compound 3.