Abstract Thermal decomposition of allyltrichlorosilane and allyltrimethylsilane at temperatures up to 1340 K were studied using flash pyrolysis coupled with molecular beam sampling and vacuum ultraviolet single-photon ionization time-of-flight mass spectrometry (VUV-SPI-TOFMS). The initial reaction of allyltrichlorosilane was homolysis of the Si-C bond, producing •SiCl3 and •C3H5 radicals. The •SiCl3 radical then underwent sequential Cl losses to form:SiCl2, SiCl and Si. The C3H5 radical also underwent secondary reactions, producing a series of C3Hx species (m/z = 39-42), consistent with previous studies. In the pyrolysis of allyltrimethylsilane, molecular elimination reaction forming Me2Si=CH2 + C3H6 and Si-C bond ruptures producing Me3Si• + •C3H5 and M e 2 S i ˙ C H 2 C H = C H 2 + •CH3 were identified as the main initiation decomposition steps. HSiMe3 was also identified as one of the initiation reaction products. The observed secondary reactions of Me2Si=CH2 and Me3Si• were consistent with previous studies. Possible thermal decomposition mechanism of the M e 2 S i ˙ C H 2 C H = C H 2 product was also proposed.

中文翻译：

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烯丙基三氯硅烷和烯丙基三甲基硅烷的热分解机理

摘要 使用快速热解结合分子束采样和真空紫外单光子电离飞行时间质谱 (VUV-SPI-TOFMS) 研究了烯丙基三氯硅烷和烯丙基三甲基硅烷在高达 1340 K 的热分解。烯丙基三氯硅烷的初始反应是 Si-C 键的均裂，产生 •SiCl3 和 •C3H5 自由基。•SiCl3 自由基随后经历连续的 Cl 损失以形成：SiCl2、SiCl 和 Si。C3H5 自由基也经历了二次反应，产生了一系列 C3Hx 物种（m/z = 39-42），与之前的研究一致。在烯丙基三甲基硅烷的热解中，分子消除反应形成 Me2Si=CH2 + C3H6 和 Si-C 键断裂产生 Me3Si• + •C3H5 和 Me 2 Si ˙ CH 2 CH = CH 2 + •CH3 被确定为主要的引发分解脚步。HSiMe3 也被确定为引发反应产物之一。观察到的 Me2Si=CH2 和 Me3Si• 的二次反应与之前的研究一致。还提出了 Me 2 S i ˙ CH 2 CH = CH 2 产物的可能热分解机制。