10026-04-7

Trimethyl- and trichlorosilylcobalt tetracarbonyls and the hydrosilation of ethylene

Baay, Yvonne Louise,MacDiarmid, Alan G.

, p. 986 - 994 (1969)

The new compound (CH3)3SiCo(CO)4 was synthesized by the reaction of (CH3)3SiH with either Co2(CO)8 or HCo(CO)4. The interaction of Cl3SiH or CH3S

Schumb, W. C.

, p. 587 - 595 (1942)

Preparation of Hexafluorodisilane and Reactions of Hexafluorodisilane and Hexachlorodisilane with Sulfur Trioxide

Suresh, Bettadapura Srinivasaiah,Padma, Doddaballapur Krishnamurthy

, p. 1867 - 1868 (1985)

Hexafluorodisilane has been prepared by the fluorination of hexachlorodisilane or hexabromodisilane by potassium fluoride in boiling acetonitrile, in yields approximating 45 and 60percent respectively.Hexafluorodisilane has been characterised by infrared

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Zemany,Price

, p. 4222 (1948)

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Tris(trichlorosilyl)tetrelide Anions and a Comparative Study of Their Donor Qualities

Teichmann, Julian,Kunkel, Chantal,Georg, Isabelle,Moxter, Maximilian,Santowski, Tobias,Bolte, Michael,Lerner, Hans-Wolfram,Bade, Stefan,Wagner, Matthias

, p. 2740 - 2744 (2019)

Trichlorosilylated tetrelides [(Cl3Si)3E]? have been prepared by adding 1 equiv of a soluble Cl? salt to (Cl3Si)4Si (E=Si) or 4 Si2Cl6/GeCl4 (E=Ge). To asse

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Rochow, E. G.

, p. 963 - 965 (1945)

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Nonclassical complex of dichlorosilylene with CO: direct spectroscopic detection

Boganov, S. E.,Egorov, M. P.,Lalov, A. V.,Promyslov, V. M.,Syroeshkin, M. A.

, p. 1084 - 1092 (2021)

A complex between SiCl2 and CO of the 1:1 composition with coordination of the silylene to the C atom of carbon monoxide is detected in Ar matrices using FTIR spectroscopy. A positive shift of the ν(CO) band of the complex relative to the corre

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Agre, C. L.,Hilling, W.

, p. 3899 - 3902 (1952)

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Interactions of chloromethyldisilanes with tetrakis(dimethylamino)ethylene (TDAE), formation of [TDAE] [Si3Me2Cl7]

Knopf,Herzog,Roewer,Brendler,Rheinwald,Lang

, p. 14 - 22 (2002)

The chlorodisilanes SiClMe2-SiClMe2 (1), SiCl2Me-SiCl2Me (2), SiCl3-SiCl3 (3) and a 9:1 mixture of 2 and SiCl3-SiCl2Me (4) were reacted with the electron-rich alkene tetrakis-(dimethylamino)-ethylene (TDAE) in n-hexane as well as in polar solvents. While 1 gave no reaction at all, 3 underwent a disproportionation reaction into SiCl4 and Si(SiCl3)4. Also 2 and mixtures of 2 and 4 were disproportionated into MeSiCl3 (2a) and methylchlorooligosilanes. Additionally a crystalline mixture of Si3Me3Cl6 -TDAE (5a) plus Si3Me2Cl7 -TDAE (5b) was obtained by reaction of a 9:1 mixture of 2 and 4 with TDAE in n-hexane as well as in 1,2-dimethoxyethane. The reaction of 2 with TDAE in acetonitrile (MeCN) led to a crystalline precipitation of [TDAE]Cl2 -MeCN (6.MeCN) in addition to MeSiCl3 and methylchlorooligosilanes. The structures of 5b and 6.MeCN were determined by X-ray crystallography beside their NMR and IR spectroscopic characterization. Compound 5b crystallizes in the monoclinic space group P2/c (Z = 4), 6.MeCN in the orthorhombic space group Pna21 (Z = 4). The structure of 5b reveals a [TDAE].+ radical cation and a 1, 2-Me2Si3Cl7- anion with a pentacoordinated central silicon atom.

Baxter, G. P.,Weatherill, P. F.,Holmer, E. O.

, p. 1194 - 1197 (1920)

Gillot, B.,Souha, H.,Viale, D.

, (1992)

Si-C coupling reaction of polychloromethanes with HSiCl3 in the presence of Bu4PCl: Convenient synthetic method for bis(chlorosilyl)methanes

Jung, Dong Euy,Kang, Seung-Hyun,Han, Joon Soo,Lim, Weon Cheol,Park, Young-ae W.,Yoo, Bok Ryul

, p. 3901 - 3906 (2007)

Coupling reaction of polychloromethanes CH4-nCln (n = 2-4) with HSiCl3 in the presence of tetrabutylphosphonium chloride (Bu4PCl) as a catalyst occurred at temperatures ranging from 30 °C to 150 °C. The reactivity of polychloromethanes increases as the number of chlorine-substituents on the carbon increases. In the reactions of CCl4 with HSiCl3, a variety of coupling products such as bis(chlorosilyl)methanes CH2(SiCl3)(SiXCl2) [X = Cl (1a), H (1b)], (chlorosilyl)trichloromthanes Cl3CSiXCl2 [X = Cl (2a), H (2b)], and (chlorosilyl)dichloromthanes Cl2HCSiXCl2 [X = Cl (3a), H (3b)] were obtained along with reductive dechlorination products such as CHCl3 and CH2Cl2 depending on the reaction temperature. In the reaction of CCl4, 2a is formed at the initial stage of the coupling reaction and converted to give CHCl3 at low temperature of 30 °C, to give 1a, 3a, and CHCl3 at 60 °C, and to afford 1a as major product and CH2Cl2 in competition above 100 °C. Si-H bond containing silylmethanes can be formed by the H-Cl exchange reaction with HSiCl3. Reaction of CHCl3 with HSiCl3 took placed at 80 °C to give three compounds 1a, 3a, and CH2Cl2, and finally 3a was converted to give 1a and CH2Cl2 at longer reaction time. While the condition for the reaction of CH2Cl2 with HSiCl3 required a much higher temperature of 150 °C. Under the optimized conditions for synthesizing bis(chlorosilyl)methanes 1a,b, a mixture of 1a and 1b were obtained as major products in 65% (1a:1b = 64:1) and 47% (42:5) yields from the reaction of CCl4 and CHCl3 at 100 °C for 8 h, respectively, and in 41% (34:7) yield from that of CH2Cl2 at 170 °C for 12 h. In the Si-C coupling reaction of polychloromethanes with HSiCl3, it seems likely that a trichlorosilyl anion generated from the reaction of HSiCl3 with Bu4PCl is an important key intermediate.

Dyke, J. M.,Lee, E. P. F.,Morris, A.,Nyulaszi, L.

, p. 175 - 188 (1993)

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Goubeau,Behr

, p. 2,6,9 (1953)

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A vapor-solid strategy to silica sheathed metal nanostructures and microstructures via reactions of metal chlorides with silicon

Wang, Jin,Zhang, Haoxu,Ge, Jianping,Li, Yadong

, p. 807 - 811 (2006)

A facile vapor-solid strategy has been developed to prepare silica-sheathed metal micro/nanostructures with controllable shapes. As examples, silica-sheathed nickel nanowires (diameter ～50 nm), microcubes (edge length 1-3 μm), nanocubes (edge length ～200 nm) with an epitaxial tail (diameter 2 structures are discussed. The method is expected to be applied to a wider range of metals.

Anderson

, p. 3049 (1947)

Etching of hexagonal SiC surfaces in chlorine-containing gas media at ambient pressure

Zinovev,Moore,Hryn,Pellin

, p. 2242 - 2251 (2006)

The modification of the silicon carbide (4H-SiC) single-crystal surface in a chlorine-containing gas mixture at high temperature (800-1000 °C) and ambient pressure was investigated. The results of silicon carbide chlorination are found to strongly depend on the hexagonal surface orientation. Due to the thermodynamically more favorable reaction of chlorine with silicon rather than carbon, the C-terminated side ( 0 0 0 over(1, -) ) clearly undergoes considerable changes, resulting in coverage by a black-colored carbon film, whereas the Si-side (0 0 0 1) surprisingly remains visually untouched. With using X-ray photoelectron spectroscopy (XPS), angle-resolved XPS and SEM it is shown that this drastic change in behavior is associated with a different structure of oxicarbide/silicate adlayer formed on the C- and Si-terminated sides of silicon carbide surface during experimental pre-treatment and air exposure. The presence of oxygen bridges connecting the silicate adlayer with the bulk SiC in the case of Si-side inhibits the chlorination reaction and makes this surface strongly resistant to chlorine attack. Only some places on the Si-terminated side demonstrate traces of chlorine etching in the form of hexagonal-shaped voids, which are possibly initiated by distortion of the initial crystalline structure by micropipes. In contrast, a thin carbon layer resulted on the C-terminated side as a consequence of the chlorination process. XPS, ARXPS, SEM and Raman spectroscopy study of created film allows us to argue that it consists mainly of sp2-bonded carbon, mostly in the form of nanoscale graphene sheets. The absence of a protective oxygen bridge between the silicate adlayer and the bulk silicon carbide crystal leads to unlimited growth of carbon film on the SiC ( 0 0 0 over(1, -) ) side.

Hyde, K. R.,Hooper, E. W.,Waters, J.,Fletcher, J. M.

, p. 428 - 434 (1965)

Souha, H.,Weber, G.,Gillot, B.

, p. 215 - 222 (1990)

Frost,Rochow

, p. 201,203 (1958)

Reactivity of Cu3Si of different genesis towards copper(I) chloride

Souha,Bernard,Gaffer,Gillot

, p. 71 - 77 (2000)

A comparative study of the reactivity between copper(I) chloride and three types of Cu3Si obtained in a molten medium (Cu3Si-Ref) and from mechanical activation following an annealing process (Cu3Si-M2AP) or a self-propagating high-temperature synthesis (Cu3Si-MASHS) was performed by thermogravimetry under vacuum using non-isothermal and isothermal methods of kinetic measurement. It was established that for the three Cu3Si/CuCl systems, the acceleration and decay stages in the temperature range 145-215°C are very closely approximated by an equation of the Prout-Tompkins type where an autocatalytic process was proposed. The lower apparent activation energy obtained for the Cu3Si-MASHS/CuCl system (63 kJ mol-1 against 68 and 78 kJ mol-1 for Cu3Si-M2AP and Cu3Si-Ref, respectively) has been attributed to a small grain size which induces nanoscale contacts between reactants and impedes CuCl to sublime. (C) 2000 Elsevier Science B.V.

Kinetics and Mechanism of the Gas Phase Thermal Decomposition of Hexachlorodisilane in the Presence of Iodine

Doncaster, Alan M.,Walsh, Robin

, (1980)

The gas phase thermal reaction of Si2Cl6 with I2 has been investigated.Product analysis reveals the formation of SiCl4 and SiCl2I2.The reaction rate was found to obey the rate equation -dI

A Mild One-Pot Reduction of Phosphine(V) Oxides Affording Phosphines(III) and Their Metal Catalysts

Kapu?niak, ?ukasz,Plessow, Philipp N.,Trzybiński, Damian,Wo?niak, Krzysztof,Hofmann, Peter,Jolly, Phillip Iain

supporting information, p. 693 - 701 (2021/04/06)

The metal-free reduction of a range of phosphine(V) oxides employing oxalyl chloride as an activating agent and hexachlorodisilane as reducing reagent has been achieved under mild reaction conditions. The method was successfully applied to the reduction of industrial waste byproduct triphenylphosphine(V) oxide, closing the phosphorus cycle to cleanly regenerate triphenylphosphine(III). Mechanistic studies and quantum chemical calculations support the attack of the dissociated chloride anion of intermediated phosphonium salt at the silicon of the disilane as the rate-limiting step for deprotection. The exquisite purity of the resultant phosphine(III) ligands after the simple removal of volatiles under reduced pressure circumvents laborious purification prior to metalation and has permitted the facile formation of important transition metal catalysts.

Silicon Tetrakis(trifluoromethanesulfonate): A Simple Neutral Silane Acting as a Soft and Hard Lewis Superacid

Driess, Matthias,Hermannsdorfer, André

supporting information, p. 13656 - 13660 (2021/05/03)

A facile synthesis and isolation of pristine silicon tetrakis(trifluoromethanesulfonate), Si(OTf)4, is reported, acting as the first neutral silicon-based Lewis superacid suitable towards soft and hard Lewis bases. Its OTf groups have a dual function: they are excellent leaving groups and modulate the degree of reactivity towards soft and hard Lewis bases. Exposed to soft Lewis donors, Si(OTf)4 leads to [L2Si(OTf)4] complexes (L=isocyanide, thioether and carbonyl compounds) with retention of all Si?OTf bonds. In contrast, it can cleave C?X bonds (X=F, Cl) of hard organic Lewis bases with a high tendency to form SiX4 (X=F, Cl) after halide/triflate exchange. Most notable, Si(OTf)4 allows a gentle oxydefluorination of mono- and bis(trifluoromethyl)benzenes, resulting in the formation of the corresponding benzoylium species, which are stabilized by the weakly coordinating [Si(OTf)6] dianion.

Method for producing chloropropyltrichlorosilane

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Paragraph 0038-0049; 0053-0059, (2020/03/14)

The invention provides an industrial production method of trichloro(3-chloropropyl)silane. A trichloro(3-chloropropyl)silane addition reaction coarse product is used as reaction substrates; the raw material reactants of chloropropene and trichlorosilane a

DISILANE-, CARBODISILANE-AND OLIGOSILANE CLEAVAGE WITH CLEAVAGE COMPOUND ACTING AS CATALYST AND HYDROGENATION SOURCE

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Page/Page column 39; 40, (2019/04/16)

The invention relates to a process for the manufacture of monosilanes of formula (I): MexSiHyClz (I), comprising: the step of subjecting a silane substrate (methyldisilanes, methyloligosilanes, or carbodisilanes) to a cleavage reaction of the silicon-silicon bond(s) or the silicon- carbon bonds in silane substrates the reaction involving a cleavage compound selected from a quaternary Group 15 onium compound R4 QX, a heterocyclic amine, a heterocyclic ammonium halide, or a mixture of R3P and RX. The starting material disilanes to be cleaved has the formula (II): MemSi2HnClo (II) The starting material oligosilanes to be cleaved have the general formula (III): MepSiqHrCIs (II I), The starting material carbodisilanes to be cleaved have the general formula (IV): (MeaSiHbCle)-CH2-(MecSiHdClf) (IV)