1873-77-4Relevant articles and documents
The thermolysis of ε-halodisilanes: A preference for 1,2-Si Si→O rearrangement or Si-O cleavage over Si=O bond formation
Roos, Christopher,McGibbon, Graham A.,Brook, Michael A.
, p. 1470 - 1479 (1996)
Tris(trimethylsilyl)-2,2,2-trifluoroethoxysilane 6, tris(trimethylsilyl)-2-fluoroethoxysilane 7, and tris(trimethylsilyl)-2-chloroethoxysilane 8 were synthesized and characterized by 1H, 13C and 29Si NMR, IR spectroscopy, and EI and CI mass spectrometry. Thermodynamic considerations would suggest that, as a result of the driving force provided by the formation of a Si-F or Si-Cl bond, the thermolyses of these compounds would lead to the formation of bis(trimethylsilyl)silanone 4. To examine this question, gas chromatography - mass spectrometry was as used a detection technique for products resulting from the high-pressure thermolyses of 6-8. The elimination of (Me3Si)3SiCl appears to be the major thermolytic pathway of decomposition for 8 at ambient or higher pressures, although it is accompanied by the formation of other products, some of which could have arisen from the addition of various halosilanes to a silanone. Neither 6 nor 7 thermolyzed cleanly; the former compound was essentially unreactive under the thermolysis temperatures used (850°C). Of the products produced in the thermolysis of 7, no evidence for the formation of the silanone was obtained. Independently, mass spectrometry was used to study unimolecular reactions of molecular ions derived from 6-8. The major route to solitary ions appears to involve a 1,2-trimethylsilyl migration from Si to O (9→10) prior to decomposition, for example, of the m/z 346 parent ion in the decomposition of 6. The preparation of the ionized silanone may be a minor pathway. Some of the other fragmentation pathways for 6-8 are discussed.
Tris(trimethylsilyl)silyllithium
Gilman, Henry,Smith, Clifford L.
, p. 91 - 101 (1968)
An investigation has been made of the relative reactivity of tris(trimethylsilyl)silyllithium (I) in an attempt to estimate the importance of (dπ-pπ) bonding involving two contiguous silicon atoms. The procedure used were: (1) a comparative metalation reaction; (2) a kinetic study; and (3) a cleavage reaction of a silicon-silicon bond. The results are not definitive; although they seem to imply that the reactivity of I is comparable to or less than that of triphenylsilyllithium. The reactivity of I, together with its ultraviolet and NMR spectra, has been explained in terms of dative π-bonding.
TRIS(TRIMETHYLSILYL)SILANE:A CATALYST FOR RADICAL MEDIATED REDUCTION REACTIONS
Lesage, M.,Chatgilialoglu, C.,Griller, D.
, p. 2733 - 2734 (1989)
Tris(trimethylsilyl)silane was an effective substitute for toxic, tributyltin hydride in free radical chain reductions of organic halides.It was used in catalytic amounts and was regenerated, in situ, by using sodium borohydride.
Process for preparing tetrakis (trimethylsily) silane and tris (trimethysilyl) silane
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Example 3, (2008/06/13)
Tetrakis(trimethylsilyl)silane is prepared by reacting tetrachlorosilane with chlorotrimethylsilane in the presence of lithium metal, adding a compound with active proton(s) to the reaction mixture for treating the residual lithium metal therewith while maintaining the mixture neutral or acidic, and separating tetrakis(trimethylsilyl)silane from the organic layer. The residual lithium metal is treated in a safe and simple manner. Reaction of the tetrakis(trimethylsilyl)silane with an alkyl lithium or alkali metal alkoxide, followed by acid hydrolysis, affords tris(trimethylsilyl)silane. The desired compounds are prepared in high yields and on an industrial scale.
