Abstract
Sector-field mass spectrometry was used to probe the fragmentation patterns of the cationic silicon chlorides Si2Cln+ (n = 1—6). For almost all Si2Cln+ ions, Si—Si fragmentation predominates the Si—Cl bond cleavage both in the metastable ion and collisional activation mass spectra. Analysis of the fragmentation patterns indicates that the long-lived radical cation Si2Cl6·+ corresponds to a complex [SiCl2·SiCl4]·+ rather than the intact molecular ion of hexachlorodisilane. The behavior of Si2Cl5+ is consistent with the formation of the (trichlorosilyl)dichlorosilyl cation Cl3SiSICl2+. Structural aspects are also discussed for the other Si2Cln+ species. A semi-quantitative analysis of the fragmentation patterns in conjunction with the literature thermochemistry data was used to estimate some thermochemical properties of the Si2Cln+ cations.
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