Correlation of hydrogen-atom abstraction reaction efficiencies for aryl radicals with their vertical electron affinities and the vertical ionization energies of the hydrogen-atom donors.

ABSTRACT: The factors that control the reactivities of aryl radicals toward hydrogen-atom donors were studied by using a dual-cell Fourier-transform ion cyclotron resonance mass spectrometer. Hydrogen-atom abstraction reaction efficiencies for two substrates, cyclohexane and isopropyl alcohol, were measured for 23 structurally different, positively charged aryl radicals, which included dehydrobenzenes, dehydronaphthalenes, dehydropyridines, and dehydro(iso)quinolines. A logarithmic correlation was found between the hydrogen-atom abstraction reaction efficiencies and the (calculated) vertical electron affinities (EA) of the aryl radicals. Transition state energies calculated for the reaction of three of the aryl radicals with isopropyl alcohol were found to correlate linearly with their (calculated)

SUBMITTER: Jing L 

PROVIDER: S-EPMC2682590 | biostudies-literature | 2008 Dec

REPOSITORIES: biostudies-literature