The masses of daughter ions resulting from metastable transitions in the first field free region of a "reversed geometry" mass spectrometer can be accurately determined through a mass analysed ion kinetic energy scan at the apparent mass at which these daughter ions travel through the magnetic sector. A combination of these mass analysed ion kinetic scans with scanning the magnetic flux allows the resolution of overlapping metastable diffuse peaks.
The mass spectra of the methyl-, trideuteromethyl-, ethyl-and pentadeuteroethylethers of 2,2'-bi~-trimethylsilylbenzhydrol are reported. The most significant ions arise from the [M -CH,]+ ion, formed by loss of a methyl radical from one of the trimethylsilyl groups. After ring formation by interaction of the siliconium ion centre with an aromatic nucleus, the ion loses (CH,),Si-OR (R = CH,, C,H,, CD, and C2Ds), giving ion m/e 223. The fragment (CH3),Si-0CH3 is also eliminated in the four ethers investigated from the ion [M -R]+. Attack of the siliconium ion centre in the [M -CH,]+ ion on the ether oxygen leads to the generation of the [(CH,),Si+OR] ion.
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