ISSN:
0044-2313
Keywords:
Organosilicon compounds
;
Cu-catalyzed reaction of silicon with bis(trichlorsilyl)dichlormethane and related compounds
;
formation of Si-chlorinated trisila- and tetrasilamethanes, 2,4 disilacyclobutanes and C-spiro-linked Disilacyclopropanes
;
crystal structure of 1,1,3,3-Tetrachlor-2,2,4,4-tetrakis(trichlorsilyl)- 1,3-disilacyclobutane (Si6C2Cl16) and 1,1,3,3,5,5,7,7-octachlor-2,2,6,6-tetrakis(trichlorsilyl)-1,3,5,7-tetrasilaspiro [3.3]-heptane (Si8C3Cl20)
;
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Description / Table of Contents:
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)2CCl21yields 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 7this type of compounds is not obtained starting from the Si-methylated derivatives 8, 9, 10, 11They Produce a number of variously Si-chlorinated and -methylated tetrasila- and trisilamethanes. However, Cl2MeSi—CCl2—SiCl3 12forms besides of Si-chlorinated trisilamethanes also the disilacyclobutanes Si6C2Cl15Me 34and cis- and trans Si6C2Cl14Me2 35 as well as the spiro-linked disilacyclobutanes Si8C3Cl19Me 36, Si8C3Cl18Me2 37. (Cl3Si)2CHCl 38 mainly yields HC(SiCl3)3 31and also the disilacyclobutanes cis- and trans-(Cl3Si)HC(SiCl2)2CH(SiCl3) 41and (Cl3Si)2C(SiCl2)2CH(SiCl3) 45the 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: αSi = 94,2°〉 85,8° = αC.The spiro-linked disilacyclobutane rings of compound4 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: αSi = 93,9°〉 84,4° = αC are comparable to those of compound 3.
Notes:
Es wird über die Umsetzungen von (Cl3Si)2CCl2 1, seiner Si-methylierten Derivate (Me3Si)2CCl2 8, Me3Si—CCl2—SiMe2Cl 9, (ClMe2Si)2CCl2 10, Me3Si—CCl2—SiMeCl2 11, Cl2MeSi—CCl2—SiCl3 12 sowie von (Cl3Si)2CHCl 38, (Cl3Si)2CClMe 39 und Me2CCl2 mit Silicium (Cu-Kat.) in der Wirbelschicht bei 300°C - von 38 und 39 auch im Festbett - berichtet. Während die Umsetzung von (Cl3Si)2CCl2 zu C(SiCl3)4 2, dem 1,1,3,3-Tetrachlor-2,2,4,4-tetrakis(trichlorsilyl)-1,3-disilacyclobutan Si6C2Cl16 3 und den C-spiro-verbrückten Disilacyclobutanen Si8C3Cl20 4, Si10C4Cl24 5, Si12C5Cl28 6, Si14C6Cl32 7 führen, wird dieser Verbindungstyp von den Si-methylierten Verbindungen 8, 9, 10, 11 nicht gebildet. Ihre Umsetzungen führen zu unterschiedlich Si-chlorierten-methylierten Tetrasila- bzw. Trisilamethanen. Dagegen bildet das Cl2MeSi—CCl2—SiCl3 12 neben Si-chlorierten Trisilamethanen die Disilacyclobutane Si6C2Cl15Me 34, Si6C2Cl14Me2 35 (cis- und trans), 4 und Si8C3Cl19Me 36, Si8C3Cl18Me2 37. (Cl3Si)2CHCl 38 bildet HC(SiCl3)3 31 (Hauptprodukt), und es entstehen die Disilacyclobutane (Cl3Si)HC(SiCl2)2CH(SiCl3) 41 (cis, trans), (Cl3Si)2C(SiCl2)2CH(SiCl3) 45, das 1,3,5-Trisilacyclohexan [Cl3Si(H)C—SiCl2]3 44 sowie (Cl3Si)2CH—CH(SiCl3)2 und [(Cl3Si)2CH]2SiCl2. Aus (Cl3Si)2CClMe 39 bilden sich bevorzugt (Cl3Si)2C=CH2 und (Cl3Si)2CHMe neben HC(SiCl3)3, MeC(SiCl3)3 und (Cl3Si)3C—SiCl2Me. Aus Me2CCl2 59 entstehen bevorzugt Me(Cl)C=CH2, Me2CHCl sowie HCl2Si—CMe2—SiCl3 neben Me2C(SiCl3)2 und Me2C(SiCl2H)2. Verbindung 3 kristallisiert triklin in der Raumgruppe P1 (Nr. 2) mit a = 900,3, b = 914,0, c = 855,3 pm, α = 116,45°, β = 101,44°, γ = 95,86° und mit einem Molekül Pro Elementarzelle; 4: monoklin in der Raumgruppe C2/c (Nr. 15) mit a = 3 158,3, b = 1 103,7, c = 2 037,4 pm, β = 116,62° und mit 8 Molekülen pro Elementarzelle. In 3 ist der Disilacyclobutanring planar mit d(Si—C) = 191,8 pm und der üblichen Deformation in den endocyclischen Winkeln αSi = 94,2°〉 85,8° = αC. Im Bicyclus 4 sind die beiden spiroverknüpften Disilacyclobutanringe leicht gefaltet (19,0°) mit d(Si—C) = 190,4 pm am Spiro-C-Atom und d(Si—C) = 192,0 pm an den beiden anderen. Auch in 4 gilt für die endocyclischen Winkel αSi = 93,9° 〉 84,4° = αC.
Additional Material:
2 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/zaac.19936190903
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