Über Silikone, XL. Die Synthese siliciumorganischer Verbindungen aus Chloroform

Müller, Richard; Seitz, G.

doi:10.1002/cber.19580910104

Cited by 53 publications

(11 citation statements)

References 6 publications

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“…As first reactivity tests, we treated [ n Bu 4 N][ A ] and [ n Bu 4 N] 2 [ B ] with anhydrous MeOH/NMe 2 Et and obtained H A OMe and H 2 B OMe in yields of 59% and 88%, respectively. By the same token, protonation with CF 3 SO 3 H selectively furnished H A and H 2 B , respectively. Both protonation reactions can also be conducted with ethereal HCl, but care must be taken to avoid partial desilylation by nucleophilic attack of Cl – .…”

Section: Resultsmentioning

confidence: 96%

Exhaustively Trichlorosilylated C₁ and C₂ Building Blocks: Beyond the Müller–Rochow Direct Process

Georg¹,

Teichmann²,

Bursch

et al. 2018

J. Am. Chem. Soc.

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The Cl-induced heterolysis of the Si-Si bond in SiCl generates an [SiCl] ion as reactive intermediate. When carried out in the presence of CCl or ClC═CCl (CHCl solutions, room temperature or below), the reaction furnishes the monocarbanion [C(SiCl)] ([A]; 92%) or the vicinal dianion [(ClSi)C-C(SiCl)] ([B]; 85%) in excellent yields. Starting from [B], the tetrasilylethane (ClSi)(H)C-C(H)(SiCl) (HB) and the tetrasilylethene (ClSi)C═C(SiCl) (B; 96%) are readily available through protonation (CFSOH) or oxidation (CuCl), respectively. Equimolar mixtures of HB/[B] or B/[B] 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 CuCl furnishes the disilylethyne ClSiC≡CSiCl (C; 80%); in the presence of [HMeN]Cl, the trisilylethene (ClSi)C═C(H)SiCl (D; 72%) is obtained. Alkyne C undergoes a [4+2]-cycloaddition reaction with 2,3-dimethyl-1,3-butadiene (CHCl, 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 (CHCl, 180 °C, 4 d). All closed-shell products were characterized by H,C{H}, and Si NMR spectroscopy; an EPR spectrum of [ nBuN][B] was recorded. The molecular structures of [ nBuN][A], [ nBuN][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], C, and D are postulated.

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Section: Resultsmentioning

confidence: 96%

Exhaustively Trichlorosilylated C₁ and C₂ Building Blocks: Beyond the Müller–Rochow Direct Process

Georg¹,

Teichmann²,

Bursch

et al. 2018

J. Am. Chem. Soc.

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“…The first route starts from bis(trichlorosilyl)acetylene (2 ), which is read ily accessible on a large as well as on a laboratory scale [17][18][19]. The compound can be reduced to disilylacetylene using phase transfer techniques …”

Section: Preparation and Properties O F The Compoundsmentioning

confidence: 99%

Synthesis and Molecular Structure of Silylated Ethenes and Acetylenes

Rüdinger

Beruda

Schmidbaur

1994

Zeitschrift Für Naturforschung B

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, By varying their stoichiometry these compounds can be used as single source feedstock gases for layers with tailor-made composition. In a new approach to the epitaxial deposition of silicon carbide, halogencontaining feedstock gases are expected to show improved properties owing to a greater reversi bility of the deposition process. W hereas polysilylalkanes halogenated at carbon are well rep resented in the literature [1 0 , 1 1 ], only limited information is available on the corresponding alkenes. The low thermal stability of polysilylated haloalkanes makes these compounds unsuitable for practical processes. The ethene analogues are expected to exhibit greater thermal stability and to be more amenable regarding storage and con * Reprint requests to Prof. Dr. H. Schmidbaur. tinuous handling. Although several sterically crowded polysilyl ethenes have been the subject of investigations of their molecular structure, dy namics and energy characteristics [12][13][14][15][16], the num ber of structurally characterized compounds is still small. Following work on silylalkanes, our more recent studies have therefore focused on silyl olefines. In the course of these investigations we have undertaken the X-ray structure determ i nations of bis(trichlorosilyl)acetylene and of the two most crowded trichlorosilylethenes, tris(trichlorosilyl)ethene and tetrakis(trichlorosilyl)-ethene.

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“…All the possible chlorinated and methylated compounds having the basic structure Si-CH2-Si have been isolated from the pyrolysis products of (CH3)3SiCI. The distribution of the 1,3disilapropanes (I 7) to (26) in the pyrolysis products of the three methylchlorosilanes are compared in Table 3. The 1,3-disilapropanes accounted for 32 % of the total pyrolysis product from (CH&SiCl, 43 % of that from (CH3)2SiC12, and 60 % of that from CH3SiC13.…”

Section: Pyrolysismentioning

confidence: 99%

“…Photochlorination leads to chlorination of the C H groups of the carbosilane skeleton, the reaction proceeding as far as steric factors allow [26,27] (cf. eqs.…”

Section: Synthesis Of Carbosilanes Containing Functional Groupsmentioning

confidence: 99%

Formation and Properties of Carbosilanes

Fritz

1967

Angew. Chem. Int. Ed. Engl.

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R = alkyl) presumably involves the direct participation of the triple bond, and, as with the allene derivatives, proceeds via a vinyl cation (99). This is supported by the fact that, despite the strong inductive effect of the triple bond, the rates of solvolysis of the acetylene derivatives (98), R = alkyl, are only slightly lowerWe are grateful to the Deutsche Forschungsgemeinschaft and to the Fonds der Chemischen Industrie for their support of our own work, which was carried out by, The present paper describes the formation of silicon-carbon compounds (carbosilanes), the moIecular skeletons of which consist of alternate Si and C atoms, and which can be obtained by thermal decomposition of Si(CH3)4, CH3SiCI3, (CH3)2SiCIz, and (CH3)3SiCl. The description of the formation of carbosilanes is followed by a discussion of the reactions of polychlorinated carbosilanes with organometallic compounds.

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Über Silikone, XL. Die Synthese siliciumorganischer Verbindungen aus Chloroform

Cited by 53 publications

References 6 publications

Exhaustively Trichlorosilylated C₁ and C₂ Building Blocks: Beyond the Müller–Rochow Direct Process

Exhaustively Trichlorosilylated C₁ and C₂ Building Blocks: Beyond the Müller–Rochow Direct Process

Synthesis and Molecular Structure of Silylated Ethenes and Acetylenes

Formation and Properties of Carbosilanes

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Über Silikone, XL. Die Synthese siliciumorganischer Verbindungen aus Chloroform

Cited by 53 publications

References 6 publications

Exhaustively Trichlorosilylated C1 and C2 Building Blocks: Beyond the Müller–Rochow Direct Process

Exhaustively Trichlorosilylated C1 and C2 Building Blocks: Beyond the Müller–Rochow Direct Process

Synthesis and Molecular Structure of Silylated Ethenes and Acetylenes

Formation and Properties of Carbosilanes

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Exhaustively Trichlorosilylated C₁ and C₂ Building Blocks: Beyond the Müller–Rochow Direct Process

Exhaustively Trichlorosilylated C₁ and C₂ Building Blocks: Beyond the Müller–Rochow Direct Process