- Surface Active Organosilicone Compounds
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The present invention relates to new organodisilanes or carbodisilanes, a process for manufacturing the same and their use, in particular, as surface active agents, especially as spreading agents.
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Page/Page column 6-7
(2008/12/09)
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- Interactions of chloromethyldisilanes with tetrakis(dimethylamino)ethylene (TDAE), formation of [TDAE] [Si3Me2Cl7]
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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.
- Knopf,Herzog,Roewer,Brendler,Rheinwald,Lang
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- Raman and infrared vibrational spectra, ab initio calculations and normal coordinate analyses for 1,2-dimethyltetrachlorodisilane and 1,2-dimethyltetrachlorodisilane-d6
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The Raman spectra of CH3Cl2SiSiCl2CH3 and CD3Cl2SiSiCl2CD3 between 3000 and 30 cm-1 have been recorded at various temperatures. The infrared spectra at ambient temperature were recorded from 3000 to 50 cm-1. Both isotopomers exist as a mixture of gauche and anti rotamers at room temperature. The energy difference E(anti)-E(gauche) was determined from the Raman spectra as being -0.9 ± 0.2 kJ mol-1 for CH3Cl2SiSiCl2CH3 and -1.2 ± 0.2 kJ mol-1 for CD3Cl2SiSi2CD3. Assisted by ab initio calculations, the vibrational spectra have been assigned using C(2h) symmetry for the anti rotamers and C2 symmetry for the gauche rotamers. Scaled and unscaled harmonic frequencies and harmonic symmetry force constants have been reported for both rotamers, and normal coordinate analyses have been carried out. Potential energy distributions have been reported.
- Ernst, Margot,Schenzel, Karla,Jaehn, Anke,Hassler, Karl
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- Methylchlorooligosilanes as products of the basecatalysed disproportionation of various methylchlorodisilanes
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The methylchlorodisilanes SiCl2Me-SiCl2Me (1), SiCl2Me-SiClMe2 (2) and SiClMe2-SiClMe2 (3) disproportionate in the presence of a basic catalyst into methylchloromonosilanes and various methylchlorooligosilanes. Oligosilanes involving up to seven silicon atoms were identified by means of 29Si-, 13C-1H-NMR and GC-MS measurements. Formation of methylchlorooligosilanes is thought to take place via silylene intermediates.
- Herzog,Richter,Brendler,Roewer
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p. 221 - 228
(2007/10/03)
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- AEQUILIBRIERUNGSREAKTIONEN AN DISILANEN
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Redistribution reactions of Si2Me6 and Si2Cl6 and of Si2Me2Cl4 and Si2Me2H4 are discussed.While the high temperature necessary for the exchange between methyl and chlorine leads to rupture of the silicon-silicon bond in the case of the Si2Me6/Si2Cl6 system, redistribution of chlorine and hydrogen proceeds at room temperature with AlCl3 as catalyst.The reaction between Si2Me2Cl4 and Si2Me2H4 at 90 deg C is examined in detail by 1H NMR spectroscopy.This reaction is a useful route for preparation of the new compounds Me2Si2ClxH4-x (x=1-3). 1H NMR, 13C NMR, 29Si NMR, IR and Raman spectroscopic data of the partly unknown 1,2-dimethylchlorodisilanes are reported.
- Schmoelzer, H.,Hengge, E.
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- Atrane Analogous Compounds of the Type (I)
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Heterocyclic cage compounds of type I (compounds 8 - 10) have been prepared by condensation reactions of 1,2,2-trifunctional disilanes Me(R)XSiSiMeX2 (R = Me, Ph, OEt; X = NMe2, OEt) with triethanolamine using the "Dilution Principle".The starting compounds are obtained by Si - Me cleavage of Si2Me6 with acetylchloride/AlCl3 followed by either aminolysis with HNMe2 or alcoholysis with EtOH. 1H NMR spectra indicate N -> Si(1) intraction with the more acidic Si atom in 8 and 9.This result is proved by the X-ray structure analysis of 8 (monoclinic, P 21/c; a = 7.088(2), b = 15.070(4), c = 12.701(4) Angstroem, β = 104.96(2) at -130 deg C, Z = 4); the Si(1) *** N distance is found to be 2.768 Angstroem, connected with a significant angular distortion of the tetrahedral coordination around Si(1) towards a trigonal bipyramid.In compound 10, too, N -> Si(1) coordination is observed at room temperature in spite of almost equal acidity for both Si atoms.This can be explained by the preference of 5- over 6-membered chelating ring systems.At higher temperatures the 1H NMR spectra show a fluctuation of the N-donor between the two Si centres. - Key words: Silatranes, Transanular N -> Si-Interactions, NMR Spectra, X-Ray
- Grobe, Joseph,Henkel, Gerald,Krebs, Bernt,Voulgarakis, Nikolaos
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p. 341 - 351
(2007/10/02)
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- The synthesis of novel chlorosilyl and chlorogermyl mercurials with some of their chemical reactions
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When a mercury alkyl is irradiated in the presence of trichlorosilane, bis(trichlorosilyl)mercury, a white crystalline solid, and the alkane are formed. In a similar reaction with methyldichlorosilane, bis(methyldichlorosilyl)mercury is a product. With trichlorogermane as a reactant a similar light-induced reaction produces bis(trichlorogermyl)mercury. These novel mercurials react with compounds possessing a silicon-hydrogen bond to form disilanes. Preparations are described for methylpentachlorodisilane, 1,1-dimethyltetrachlorodisilane, 1,2-dimethyltetrachlorodisilane, 1,1,1,-trimethyltrichlorodisilane, 1,1,2-trimethyltrichlorodisilane, 1,1,1,2-tetramethyldichlorodisilane, 1,1,2,2-tetramethyldichlorodisilane, pentamethylchlorodisilane, trichlorosilyltrichlorogermane, and trimethylsilylmethyltrichlorogermane using various modifications of this reaction. Syntheses have been devised for the mercurials, bis(trichlorosilyl)mercury, bis(methyldichlorosilyl)mercury, bis(trichlorogermyl)mercury, and (trimethylsilylmethyl)trichlorogermylmercury. Bis(dimethylchlorosilyl)mercury is formed at low temperatures but decomposes at temperatures above -79°. Bis(trichlorosilyl)mercury also reacts with dimanganese decacarbonyl to form trichlorosilylmanganese pentacarbonyl.
- Bettler, Charles R.,Sendra, Joseph C.,Urry, Grant
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p. 1060 - 1065
(2007/10/05)
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