Intermolecular photoreductions of ketones

Formation, structure (stereochimie et stereodynamique), et donnees de spectroscopie RMN des composes du titre

Molecular and electronic structure of penta- and hexacoordinate silicon compounds

Silicon chemical vapor deposition one step at a time: fundamental studies of silicon hydride chemistry

The homogeneous gas-phase decomposition kinetics of silane has been investigated using the single-pulse shock tube comparative rate technique (T = 1035–1184˚K, Ptotal ≈ 4000 Torr) The initial reaction of the decomposition SiH4 SiH2 + H2 is a unimolecular process in its pressure fall-off regime with experimental Arrhenius parameters of logk1 (sec−1) = 1333 ± 028–52,700 ± 1400/2303RT The decomposition has also been studied at lower temperatures by conventional methods The results confirm the total pressure effect, indicate a small but not negligible extent of induced reaction, and show that the decomposition is first order in silane at constant total pressures RRKM-pressure fall-off calculations for four different transition-state models are reported, and good agreement with all the data is obtained with a model whose high-pressure parameters are logA1 (sec−1) = 155, E1(∞) = 569 kcal, and ΔE0±0(1) = 559 kcal The mechanism of the decomposition is discussed, and it is concluded that hydrogen atoms are not involved It is further suggested that silylene in the pure silane pyrolysis ultimately reacts with itself to give hydrogen: 2SiH2 → (Si2H4)* → (SiH3SiH)* → Si2H2 + H2 The mechanism of H ⟷ D exchange absorbed in the pyrolysis of SiD4-hydrocarbon systems is also discussed

Kinetics and mechanism of the silane decomposition

Morey A. Ring

Papers

Pyrolysis of monosilane

Kinetics of the silane and silylene decompositions under shock tube conditions

New 1:1 adduct of trimethylamine and trichlorosilane, trimethylammonium trichlorosilyl

Primary and secondary rate processes in the acetone-silane photochemical system