Siloxanes as sources of silanones

Chernyshev, E. A.; Krasnova, T. L.; Sergeev, A. P.; Abramova, E. S.

doi:10.1007/bf02502945

Cited by 10 publications

(11 citation statements)

References 1 publication

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“…The stability of HMDSO has to be considered, because if formed it would have been an indicator of the occurrence of process (3) in the decomposition of L3. The pyrolysis of HMDSO has been studied by Chernyshev et al 21 at 973 K in a flow reactor. The products include tetramethylsilane (TMS) and hexamethyldisilane (HMDS) as well as several cyclic and linear polysiloxanes.…”

Section: Mechanistic Studies (Theoretical Calculations)mentioning

confidence: 99%

A mechanistic study of the low pressure pyrolysis of linear siloxanes

Almond

Becerra

Bowes

et al. 2009

Phys. Chem. Chem. Phys.

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Matrix isolation IR spectroscopy has been used to study the vacuum pyrolysis of 1,1,3,3-tetramethyldisiloxane (L1), 1,1,3,3,5,5-hexamethyltrisiloxane (L2) and 3H,5H-octamethyltetrasiloxane (L3) at ca. 1000 K in a flow reactor at low pressures. The hydrocarbons CH3, CH4, C2H2, C2H4, and C2H6 were observed as prominent pyrolysis products in all three systems, and amongst the weaker features are bands arising from the methylsilanes Me2SiH2 (for L1 and L2) and Me3SiH (for L3). The fundamental of SiO was also observed very weakly. By use of quantum chemical calculations combined with earlier kinetic models, mechanisms have been proposed involving the intermediacy of silanones Me2Si=O and MeSiH=O. Model calculations on the decomposition pathways of H3SiOSiH3 and H3SiOSiH2OSiH3 show that silanone elimination is favoured over silylene extrusion.

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Section: Mechanistic Studies (Theoretical Calculations)mentioning

confidence: 99%

A mechanistic study of the low pressure pyrolysis of linear siloxanes

Almond

Becerra

Bowes

et al. 2009

Phys. Chem. Chem. Phys.

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“…Apparently, such a spectrum reflects a complex composition of the gas phase formed by a large number of molecules with various chemical bonds: Si-O-Si (1000-1100 cm −1 , Si-C-Si and Si-O-C (900-1100 cm −1 3 9 and Si-C in the range of 800 cm −1 . 23 The HMDSO pyrolysis study demonstrates [24][25][26] that the transformation begins with the siloxane bonds break with formation of a silyl radical and a silanone molecule:…”

Section: Resultsmentioning

confidence: 99%

A Study of Pyrolysis of Polymethylsiloxanes by Fourier Transform Infrared

Alexandrov¹,

La²,

As³

2011

J. Nanosci. Nanotech.

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This paper is dedicated to a comparative study of pyrolysis of decamethylcyclopentasiloxane and hexamethyldisiloxane, widely used as precursors for CVD of silicon dioxide films. The pyrolysis process was carried out in a hot-wall horizontal tube reactor made from quartz within the temperature range 25-1000 degrees C. FTIR spectroscopy has been used for the analysis of gaseous reaction products in the exhaust line of the reactor. It has been found that transformation of DMPSO was initiated by the open ring in the precursor molecules with its further transformation to linear biradicals followed by the chain's growth due to radical reactions. HMDSO transformation is connected with separation of silanon, silyl and methyl radicals with following multi-type interactions of siloxane radicals and formation of non-rigorously organized three-dimensional molecules.

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“…Given that the “Sila‐McMurry” reaction is comparatively slow, any liberated Cl 2 SiO is likely unable to stabilize itself through direct oligomerization, because the concentration of this species at any point in time should be too low. It is thus more plausible to assume that most Cl 2 SiO consumes further Si 2 Cl 6 , which would immediately explain why more than the stoichiometric amount of the disilane is required for the full conversion of A to M .…”

Section: Methodsmentioning

confidence: 99%

Tetraarylethylenes from Diarylmethanones and Hexachlorodisilane: The “Sila‐McMurry” Reaction

Moxter

Tillmann

Füser

et al. 2016

Chemistry A European J

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Hexachlorodisilane reacts with diarylmethanones (aryl=C H , 4-MeC H , 4-tBuC H , 4-ClC H , 4-BrC H ) to furnish the corresponding tetraarylethylenes in good yields. The reductive conversion requires temperatures of about 160 °C and reaction times of 60-72 h. In the initial step, the Lewis-basic carbonyl groups likely generate low-valent [SiCl ] as an analogue of [TiCl ] in the classical McMurry reaction. The coupling sequence further proceeds via benzopinacolones, which have been isolated as key intermediates.

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Siloxanes as sources of silanones

Cited by 10 publications

References 1 publication

A mechanistic study of the low pressure pyrolysis of linear siloxanes

A mechanistic study of the low pressure pyrolysis of linear siloxanes

A Study of Pyrolysis of Polymethylsiloxanes by Fourier Transform Infrared

Tetraarylethylenes from Diarylmethanones and Hexachlorodisilane: The “Sila‐McMurry” Reaction

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