Ion/molecule reactions with pyridine (Py) of several gaseous silylium ions (Me3Si(+), Cl3Si(+), Br3Si(+), and bridgehead 3,5,7-trimethyl-1,3,5,7-tetrasilaadamant-1-yl cation), carbocations (tBu(+), iPr(+), Et+, (MeO)(2)CH+, CCl3+, CF3+, Ph+, PhCH2+, and C7H7+, and 3,5-dimethyl-1-adamantyl cation), and the dicoordinated boron cation B(OMe)(2)(+) were investigated. The silylium cations, including the unprecedented bridgehead 3,5,7-trimethyl-1,3,5,7-tetrasilaadamantyl gaseous ion, reacted to form mainly the adduct [R3Si-Py](+) via electrophilic attack. Alkyl cations (tBu(+), iPr(+), and Et+) reacted to give mainly [PyH](+) via P-elimination. CCl3+ forms both [PY-CCl3](+) and [PyH](+), whereas [PyH](+) was the dominant product for the reactions of Ph+, P-Cl-C6H4+, p-H2N-C6H4, phCH(2)(+), and the tropylium ion (Tr). The 3,5-dimethyl-1-adamantyl cation was found to be nearly unreactive towards pyridine. The (MeO)(2)B+ ion gave a set of three major products: the adduct [(MeO)(2)B-Py](+), [PyH](+), and [PyMe](+). Reactions involving isotopically labeled pyridine-d5 and CD3CD2+ were used to investigate the source of protons leading to [PyH](+) in reactions of protic and aprotic cations. Great variations of intrinsic reactivity were observed for the cations investigated, even within the same class. These changes were also found difficult to predict, as they were not always in accord with those predicted based on calculated (DFT) reaction thermochemistries. (c) 2007 Elsevier B.V. All rights reserved.