FORMATION OF ORGANOSILICON COMPOUNDS .110 . REACTIONS OF (CL3SI)2CCL2AND 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 1 1, 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 bed reactor) are presented. While (Cl3Si)2CCl2 1 yields C(SiCl3), 2, the 4,4-tetrakis(tri-chlorsilyl)-1,3-disilacycl obutane Si6C2Cl16 3 and the related C-spiro linked disilacyclobutanes Si8C3Cl20 4, Si10C4Cl24 5, Si12C5Cl28 6 and Si14C6Cl32 7, this type of compounds is not obtained starting from the Si-methylated derivatives 8, 9, 10 or 11. They produce a number of variously Si-chlorinated and -methylated tetrasila- and trisilamethanes. However, Cl2MeSi-CCl2-SiC l3 12 forms besides of Si-chlorinated trisilamethanes also the disilac yclobutanes Si6C2Cl15Me 34 and cis- and trans Si6C2Cl14Me2 35 as well as the spiro-linked disilacyclobutanes 4, Si8C3Cl19Me 36 and Si8C3Cl18 Me2 37. (Cl3Si)2CHCl 38 mainly yields HC(SiCl3), 31 and also the disil acyclobutanes cis- and trans-(Cl3Si)HC(SiCl2)2C(SiCl3)H 41 and (Cl3Si) 2C(SiCl)2C(SiCl3)H 45, the 1,3,5-trisilacyclohexane [(Cl3Si)HC-SiCl2]3 44 as well as (Cl3Si)2CH-CH(SiCl3)2 and [(Cl3Si)2CH]2SiCl2. (Cl3Si)2C ClMe 39 mainly yields (Cl3Si)2C=CH2 and (Cl3Si)2CHMe besides of HC(SiC l3)3, MeC(SiCl3)3 and Cl2MeSiC(SiCl3)3. 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 BAR (no. 2) with a = 900.3, b = 914.0, c = 855.3 pm, alpha = 116.45-de grees, beta = 101.44-degrees, gamma = 95.86-degrees and one molecule p er unit cell. Compound 4 crystallizes monoclinically in the space grou p C2/c (no. 15) with a = 3 158.3, b = 1 103.7, c = 2 037.4 pm, beta = 116.62-degrees and 8 molecules per unit cell. The disilacyclobutane ri ng of compound 3 is plane, showing a mean distance of d(Si-C)BAR = 191 .8 pm and the usual deformations of endocyclic angles: alpha(Si) = 94. 2-degrees > 85.8-degrees = alpha(C). The spiro-linked disilacyclobutan e rings of compound 4 are slightly folded by a mean angle of (19.0-deg rees). Their mean distances were found to be d(Si-C)BAR = 190.4 pm rel ating to the central carbon atom and 192.0 pm to the outer ones, respe ctively. The deformations of endocyclic angles: alpha(Si) = 93.9-degre es > 84.4-degrees = alpha(C) are comparable to those of compound 3.