Abstract
The unimolecular metastable decompositions of ethoxytrimethylsilane ((CH3)3SiOCH2CH3; 1, MW: 118) and its fluorine analogue, 2,2,2-trifluoroethoxytrimethylsilane ((CH3)3SiOCH2CF3, 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+ · is different from that of 2+ · , except for the loss of CH3 from the corresponding molecular ions. The MIKE spectra of the [M - CH3]+ ions from 1+ · and 2+ · gave five and three fragment ions, respectively. Two of the five reactions for 1 leading to the formation of the ion at m/z 101, (CH3)2Si+OCH = CH2, and m/z 61, CH3Si+HOH, concern new mechanistic pathways, which were not described in previous reports. Skeletal rearrangement by among others F and CF3 migrations, occurs during the fragmentation of the [M - CH3]+ ions from 2+ · . The m/z 61 ions from 2+ · are both CH2OCF+ (or CH2FCO+ etc.) and CH3Si+HOH.
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