Influence of hydrogen bonding on hydrogen-atom abstraction reactions of dehydropyridinium cations in the gas phase.

ABSTRACT: The reactions of several substituted, positively charged dehydropyridinium cations with cyclohexane, methanol, and tetrahydrofuran have been examined in a Fourier-transform ion cyclotron resonance mass spectrometer. All of the charged monoradicals react with the neutral reagents exclusively via hydrogen atom abstraction. For cyclohexane, there is a good correlation between the reaction efficiencies and the calculated electron affinities at the radical sites; that is, the greater the electron affinity of the charged monoradical at the radical site, the faster the reaction. The reaction efficiencies with methanol and tetrahydrofuran, however, do not correlate with the calculated electron affinities. Density functional theory (DFT) calculations indicate that for these reagents a stabilizing h

SUBMITTER: Adeuya A 

PROVIDER: S-EPMC3014263 | biostudies-literature | 2010 Dec

REPOSITORIES: biostudies-literature