The results of a study of the gas-phase reactions of unsaturated carbocations, such as the CH3CO+ ion from gamma-radiolysis of CH3F/CO mixtures, and the C6H4TCO+ ion from the beta-decay of 1,4-ditritiobenzene in the presence of CO, with pyrrole, N-methylpyrrole, furan, and thiophene, are reported. In all systems investigated, acylated heteroarenes represent the predominant reaction products, accompanied by the methylated derivatives in the CH3F/CO radiolytic mixtures, and by the phenylated ones in the 1,4-ditritiobenzene/CO decay samples. All substrates investigated are found to undergo predominant alpha-substitution by both acetyl (88.6-98.4% (pyrrole); 90.8-98.7% (N-methylpyrrole); 97.2-98.9% (furan); 94.9-98.6% (thiophene)) and benzoyl cations (92.6-96.5% (pyrrole)) under all conditions. The predominant formation of the alpha-acylated pyrroles from both reactants (> 88%), whose relative yields appear unaffected within the temperature interval from 303 to 383 K, indicates, in agreement with ancillary FT-ICR mass spectrometric evidence, that gas-phase acylation reactions toward simple five-membered heteroarenes proceed via a two-step substitution mechanism, involving a quasi-resonant single-electron transfer (SET) step followed by recombination of the ensuing radical - radical ion pair. By virtue of this entropy-favored mechanism, gaseous electrophiles with relatively high SCF STO-3G calculated LUMO energies such as CH3CO+ and C6H4TCO+ are effectively oriented toward the "soft" C(alpha) sites of the selected heteroarenes, at variance with Klopman's Charge and Frontier Orbital Control predictions. The behavior of gaseous acylating reactants toward simple heteroarenes is discussed and compared with that of other gaseous electrophiles, whose reactivity appears instead in qualitative agreement with Klopman's model.
