Abstract
Gas-phase chemistry of N-methyl 2- and 4-trimethylsilylmethylpyridinium ions 8 and 20 and the deuterated derivatives 17 and 21 was investigated using electrospray ionization (ESI) and tandem mass spectrometry. Collision-induced ionization (CID) of the derived ions m/z 180 from both 8 and 20 gave rise to (CH3)3Si+ at m/z 73 in addition to ions at m/z 108 and 106 arising from competing proton transfer and hydride transfer pathways from within the initially formed ion−molecule complexes. CID of the derived ions m/z 189 from the deuterated derivatives 17 and 21 gave rise to (CD3)3Si+ at m/z 82, in addition to ions at m/z 109 and 106. Formation of the m/z 108 ions from 8 and 20 provides evidence to support the proposed mechanism for desilylation of β-silyl carbenium ions in solution. Computational studies at B3LYP/6-311g(d,p) support the MS studies, as it was found that the favored pathway is the proton transfer from the (CH3)3Si+ ion to the basic enamine intermediate, giving rise to N-methylpicoline and silyl...
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