Rearrangement vs. dissociation of gaseous silicon-containing cations: a combined experimental–theoretical approach

The dissociative ionizations of p-MeC6H4O[CH2]2SiMe3, MeCH(Cl)SiMe2Cl, and Me[CH2]2SiMe2Cl were studied in the gas phase, experimentally by using tandem mass spectrometric techniques (MS/MS) and computationally by ab initio M.O. methods, revealing a complex scheme of rearrangements that interconvert the resulting isomeric C5H13Si+ ions, including silicenium ions and α- and β-silyl substituted carbocations.