Unimolecular Gas-Phase Reactions of Ionized Organo-Silicon Compounds. Part XVI. (CH_3)_3SiOCH_2CH_3 and (CH)3)_3SiOCH_2CF_3

Susumu Tajima; Yuko Hiroi; Satoshi NakajimaNico.M.M.Nibbering

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Unimolecular Gas-Phase Reactions of Ionized Organo-Silicon Compounds. Part XVI. (CH_3)_3SiOCH_2CH_3 and (CH)3)_3SiOCH_2CF_3

机译：电离有机硅化合物的单分子气相反应。第十六部分（CH_3）_3SiOCH_2CH_3和（CH）3_3SiOCH_2CF_3

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The unimolecular metastable decompositions of ethoxytrimethylsilane ((CH)3)_3SiOCH_2CH_3; 1,MW: 118) and its fluorine analogue, 2,2,2-trifluoroethoxtrimethylsilane ((CH-3)_3SiOCH_2CF_3, 2; MW: 172) induced by electron ionization, have been investigated by use of mass-analyzed ion kinetic energy (MIKE) spectrometry and D-labeling. Both molecular ions are formed in low abundance. The fragmentation of 1~+centre dot is different form that of 2~+centre dot , except for the loss of CH_3 from the corresponding molecular ions. The MIKE spectra of the M-CH_3~+ the formation of the ion at m/z 101, (CH_3)_2Si~+OCH=CH_2, and m/z 61, CH_3Si~+HOH, concern new mechanistic pathways, which were not described in previous reports. Skeketal rearrangement by among others F and CF_3 migrations, occurs during the fragmentation of the M-CH_3~+ ions from 2~+centre dot . The m/z 61 ions from 2~+centre dot are both CH_2OCRF~+ (or CH_2FCO~+ etc.) and CH_3SiHOH.

机译：乙氧基三甲基硅烷（（CH）3）_3SiOCH_2CH_3的单分子亚稳态分解;1，分子量：118）及其氟类似物2,2,2-三氟乙氧基三甲基硅烷（（CH-3）_3SiOCH_2CF_3,2;MW：172）由电子电离诱导，已通过使用质量分析离子动能（MIKE）光谱法和D标记进行了研究。两种分子离子都是以低丰度形成的。1~+中心点的碎裂与2~+中心点的碎裂形式不同，只是从相应的分子离子中损失了CH_3。[M-CH_3]~+ 在 m/z 101 处形成离子的 MIKE 谱图（CH_3）_2Si~+OCH=CH_2 和 m/z 61 CH_3Si~+HOH 涉及新的机理途径，这在以前的报告中没有描述过。除其他外，通过F和CF_3迁移的骨架重排发生在[M-CH_3]~+离子从2~+中心点的碎裂过程中。来自 2~+ 中心点的 m/z 61 个离子既是 CH_2OCRF~+（或 CH_2FCO~+ 等），又是CH_3SiHOH。

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《質量分析》 |2003年第4期|466-471|共6页
作者
Susumu Tajima; Yuko Hiroi; Satoshi NakajimaNico.M.M.Nibbering;
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Chemistry and Materials Science, Gunma National College of Technology (580 Toriba, Maebadhi, Gunma 371-8530, Japan);

Laser Centre and Chemistry Deprtment, vrije Universiteit (De Boelelaan 1083, 1081 HV, Amsterdam, The Netherlands);

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Unimolecular Gas-Phase Reactions of Ionized Organo-Silicon Compounds. Part XVI. (CH_3)_3SiOCH_2CH_3 and (CH)3)_3SiOCH_2CF_3

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