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

Abstract

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.