Abstract
AbstractThresholds for the appearance of fragment ions allowed the estimation of threshold fragmentation energies (TFE) for the collisionally activated dissociation (CAD) in the gas phase of laser‐desorbed pyridine‐ring substituted N‐benzylpyridinium cations to form pyridine and a carbocation. p‐Methylbenzylpyridinium cation underwent an alternative CAD into pyridinium cation and the p‐quinodimethane. The TFE are discussed in comparison with the energy differences (ΔΔHf = ΔHf(Py) + ΔHf(R+) − ΔHf(Py +R) calculated by the AM1 method to provide strong evidence for benzyl to tropylium cation rearrangement in an ion‐molecule pair.
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