Reactions of SiCl2 with N2O, NO and O2
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Abstract
The thermal route to dichlorosilylene by pyrolysis of Si2Cl6 has been investigated using both mass spectrometry and matrix isolation techniques. The formation of SiCl2 in the gas phase was confirmed by employing a known “trapping” agent, namely buta-1,3-diene, which gave the product 1,2-dichloro-1-silacyclopent-3-ene. Dichlorosilylene was then reacted with N2O and NO. The observed products in the mass spectrum from the N2O reaction were SiCl2O and its polymers and N2. On reacting SiCl2 with NO, SiCl2O and its polymers, Cl2 and N2O were all observed. Infrared spectra of argon matrices supported these findings from mass spectrometry. A mechanism is proposed for this reaction based on these observations involving the intermediacy of cyclo-Cl2SiO2 and is supported by ab initio calculations at the MP2 and G3 levels. The reaction between SiCl2 and O2 has also been investigated. The products seen in this case were SiCl2O and Cl2. Ab initio calculations again suggest that cyclo-Cl2SiO2 is involved, and a chain mechanism seems the most likely route to Cl2 formation. The calculations lead to ΔHf° (SiO2,g) = −276 ± 6 kJ mol−1.
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