Mechanism of the thermal decomposition of tetramethylsilane: a flash pyrolysis vacuum ultraviolet photoionization time-of-flight mass spectrometry and density functional theory study
文献信息
Xinghua Liu, Alexis Vazquez, Daxi Wang
The thermal decomposition of tetramethylsilane (TMS) was studied over the temperature range of 298–1450 K by combining flash pyrolysis vacuum ultraviolet photoionization time-of-flight mass spectrometry (VUV-PI-TOFMS) and density functional theory (DFT). The initial step in TMS pyrolysis produced a methyl radical (Me˙) and Me3Si˙. Me3Si˙ underwent subsequent loss of a hydrogen atom to form Me2SiCH2 and loss of a methyl radical to form Me2Si:. Isomerizations via 1,2-shift and H2 eliminations were major secondary decomposition reactions of Me2SiCH2 and Me2Si:. Among the various isomers, silylene species containing Si–H bonds, such as :Si(H)CH2CH2CH3, :Si(H)CH2CHCH2, :Si(H)CH2CH3, and :Si(H)CHCH2, played an important role in H2 elimination reactions. On the other hand, silene species were insignificant in H2 eliminations. Unlike the silylene species, H2 elimination of :SiCH2 was energetically unfavorable.
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Photochemical & Photobiological Sciences

Angewandte Chemie International Edition

Advanced Engineering Materials

Physical Chemistry Chemical Physics

Foundations of Chemistry

Current Pharmaceutical Biotechnology

Molecular Diversity

Environmental Toxicology and Pharmacology

Green Chemistry

Journal of Medical Biochemistry
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Physical Chemistry Chemical Physics

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