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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) EAs. No correlation was found between the hydrogen-atom abstraction reaction efficiencies and the (calculated) enthalpy changes for the reactions. Measurement of the reaction efficiencies for the reactions of 15 different hydrogen-atom donors with two selected aryl radicals revealed a logarithmic correlation between the hydrogen-atom abstraction reaction efficiencies and the vertical ionization energies (IE) of the hydrogen-atom donors, but not the lowest homolytic X-H (X = heavy atom) bond dissociation energies of the hydrogen-atom donors. Examination of the hydrogen-atom abstraction reactions of 29 different aryl radicals and 18 different hydrogen-atom donors showed that the reaction efficiency increases (logarithmically) as the difference between the IE of the hydrogen-atom donor and the EA of the aryl radical decreases. This dependence is likely to result from the increasing polarization, and concomitant stabilization, of the transition state. Thus, the hydrogen-atom abstraction reaction efficiency for an aryl radical can be "tuned" by structural changes that influence either the vertical EA of the aryl radical or the vertical IE of the hydrogen atom donor.

SUBMITTER: Jing L

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

REPOSITORIES: biostudies-literature

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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.

Jing Linhong L Nash John J JJ Kenttämaa Hilkka I HI

Journal of the American Chemical Society 20081201 52

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 b ...[more]

PMID: 19061320

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Project description:H-Abstraction reactions occurring during electron impact ionization processes in electron ionization mass spectrometry (EI-MS) are a long-standing and crucial topic in MS research. Yet, some critical relevant mechanisms are controversial and ambiguous, and information about the EI-induced H-abstraction reactions of halogenated organic compounds (HOCs) is completely in the dark. This study provides a systematic investigation of H-abstraction reactions of HOCs taking place in the EI source using 13C6-hexachlorobenzene (13C6-HCB) and 13C6-hexabromobenzene (13C6-HBB) as exemplary compounds by gas chromatography (GC)-high-resolution mass spectrometry (GC-HRMS). The H-abstraction efficiencies were evaluated with the MS signal intensity ratios of ions with H-abstraction relative to the corresponding original ions (without H-abstraction). Ion source temperatures, EI energies, and numbers of heavy isotope atoms (37Cl or 81Br) of isotopologues were investigated in terms of their effects on the H-abstraction efficiencies. The H-abstraction efficiencies of individual isotopologues generally decreased from the first to the last isotopologues of respective ions, and those of individual ions were different from each other, with the highest values of 0.017 and 0.444 for 13C6-HCB and 13C6-HBB, respectively. The overall H-abstraction efficiencies involving all measured ions of 13C6-HCB and 13C6-HBB were 0.004 and 0.128, respectively. With increasing ion source temperatures, the H-abstraction efficiencies first increased to a summit and then began to linearly decrease. EI energies and emission currents could impact the H-abstraction efficiencies but showed no certain tendency. The H-abstraction reactions were inferred to belong to ion-molecule reactions, and the siloxanes bleeding from the GC column might be a hydrogen source. Some strategies were proposed for eliminating or alleviating the interference triggered by the H-abstraction reactions in EI-MS in identification of halogenated organic pollutants (HOPs). Our findings provide a better understanding of the EI-induced H-abstraction reactions of HOCs and may benefit the identification of HOPs in environmental analysis, especially for novel HOPs.

Dataset Information

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.

Publications

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.

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