The kinetics and mechanism of the shock induced gas phase decomposition of ethylsilane

Abstract

The decomposition kinetics of ethylsilane under shock tube conditions (P, ca. 3100

IR laser­induced thermolysis and UV laser­induced photolysis of 1,3­diethyldisiloxane: chemical vapour deposition of nanotextured hydridoalkylsilicones

“…We note that these steps were also observed in the thermolysis of structurally similar monoorganosilanes: the infrared multiphoton decomposition of monoalkylsilanes was proposed to occur via a fourcentre elimination of silane 21,22 or 1,1-H 2 elimination, 23 and the shock-induced thermolysis of these compounds was interpreted as a blend of 1,2-H 2 and 1,1-H 2 elimination. 24,25 The minor extent of disiloxane decomposition via elimination and polymerization of silanone H 2 SiLO is supported by the presence of silane; this reaction is a well documented process when disiloxane is exposed to TEA CO 2 laser radiation. 14,26 Ethylsilane having been not observed among the products indicates that this mode of decomposition of DEDSO and of ethyldisiloxane into ethylsilane and silanones (e.g.…”

“…Routes A and B of the DEDSO decomposition in Scheme 1 lead to different final products; the former affords perhydridosilicone, while the latter yields a silicone polymer incorporating some Si-Si bonds and ethyl and H substituents. Route B affords various silylenes which can be inferred 24,25 to undergo insertions into Si-H bonds of DEDSO and of the siloxanes produced by elimination of silanes from these products of insertion. These reactions make the total scheme of the formation of solid macromolecules rather complex.…”

Diethylsilane on silicon surfaces: Adsorption and decomposition kinetics

“…Although ethylene has been monitored during the gas phase pyrolysis of ethylsilanc, 13,14 this is the first observation of f:J-hydride elimination from a silicon atom on a silicon surface. The presence of ethylene in the desorption yield suggests that the ethyl groups on the silicon surface decompose via a ,6~hydride elimination reaction.…”

“…13. The energy required to break a C-H, C-C, and Si-C bond and form a C-=C and Si-H bond is approximately 34 kcallmol.…”

Kinetics of the Thermal Decomposition of Ethylsilane: Shock-Tube and Modeling Study

“…Since the reactive silylene intermediate SiH 2 was found to significantly influence the overall EtSiH 3 decomposition kinetics, ethyne (C 2 H 2 ) was used as a silylene scavenger. Rickborn et al derived a rate constant expression of k [EtSiH 3 ⇄ H 2 + HSiC 2 H 5 ] = 1.38 × 10 15 s –1 exp­(−271 kJ mol –1 / RT ). With a gas chromatograph (GC) equipped with a flame-ionization detector (FID), ethylene (C 2 H 4 ) and monosilane (SiH 4 ) were the only products that could be identified and quantified.…”