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Fragmentation and rearrangement processes in the high resolution mass spectra of diphenylsilyl compounds
Author(s) -
Ho Benedic T. Y. K.,
Spialter Leonard,
Smithson Lee D.
Publication year - 1975
Publication title -
organic mass spectrometry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.475
H-Index - 121
eISSN - 1096-9888
pISSN - 0030-493X
DOI - 10.1002/oms.1210100506
Subject(s) - fragmentation (computing) , mass spectrum , chemistry , metastability , ion , radical ion , high resolution , geminal , rearrangement reaction , biphenyl , cleavage (geology) , bond cleavage , crystallography , photochemistry , stereochemistry , materials science , organic chemistry , catalysis , remote sensing , composite material , operating system , fracture (geology) , computer science , geology
High resolution mass spectra of a series of diphenylsilyl compounds, Ph 2 SiX 2 (X=H, F, Cl) and Ph 2 Si(oy) 2 (Y=Et, Me, H), were recorded. Results from selected metastable defocusing experiments showed that if X or OY can be readily lost stepwise, the relative abundance of the biphenyl radical rearrangement ion (d) is small; if neutral silicon species such as :SiX 2 , SiX or :Si(OY) 2 are readily eliminated, the relative abundance of the ion d will be large. The ion d originates from both odd‐ and even‐electron ions, thus making the radical site mechanism, which requires a phenyl radical to polarize the other phenyl group, rather unlikely to be an important general driving force. The condensation of phenyl groups could be more appropriately viewed in terms of bond liability and product stability. In the special case of diphenylsilyl catecholate, in addition to geminal cleavage of phenyl groups, complex fragmentation and rearrangement processes were also observed.