%0 Generic %A Adeuya, Anthony %A Price, Jason M. %A Jankiewicz, Bartłomiej J. %A Nash, John J. %A Kenttämaa, Hilkka I. %D 2009 %T Gas-Phase Reactivity of Protonated 2-, 3-, and 4-Dehydropyridine Radicals Toward Organic Reagents %U https://acs.figshare.com/articles/dataset/Gas_Phase_Reactivity_of_Protonated_2_3_and_4_Dehydropyridine_Radicals_Toward_Organic_Reagents/2807047 %R 10.1021/jp901380y.s016 %2 https://acs.figshare.com/ndownloader/files/4501579 %K Charged radicals 2 %K electrophilic carbon atom %K phenyl radicals %K HCN %K resonance %K CN %K tetrahydrofuran yields products %K hydrogen atom %K iodine atom abstraction %K reactivity %K hydrogen atom abstraction %X To explore the effects of the electronic nature of charged phenyl radicals on their reactivity, reactions of the three distonic isomers of n-dehydropyridinium cation (n = 2, 3, or 4) have been investigated in the gas phase by using Fourier-transform ion cyclotron resonance mass spectrometry. All three isomers react with cyclohexane, methanol, ethanol, and 1-pentanol exclusively via hydrogen atom abstraction and with allyl iodide mainly via iodine atom abstraction, with a reaction efficiency ordering of 2 > 3 > 4. The observed reactivity ordering correlates well with the calculated vertical electron affinities of the charged radicals (i.e., the higher the vertical electron affinity, the faster the reaction). Charged radicals 2 and 3 also react with tetrahydrofuran exclusively via hydrogen atom abstraction, but the reaction of 4 with tetrahydrofuran yields products arising from nonradical reactivity. The unusual reactivity of 4 is likely to result from the contribution of an ionized carbene-type resonance structure that facilitates nucleophilic addition to the most electrophilic carbon atom (C-4) in this charged radical. The influence of such a resonance structure on the reactivity of 2 is not obvious, and this may be due to stabilizing hydrogen-bonding interactions in the transition states for this molecule. Charged radicals 2 and 3 abstract a hydrogen atom from the substituent in both phenol and toluene, but 4 abstracts a hydrogen atom from the phenyl ring, a reaction that is unprecedented for phenyl radicals. Charged radical 4 reacts with tert-butyl isocyanide mainly by hydrogen cyanide (HCN) abstraction, whereas CN abstraction is the principal reaction for 2 and 3. The different reactivity observed for 4 (as compared to 2 and 3) is likely to result from different charge and spin distributions of the reaction intermediates for these charged radicals. %I ACS Publications