Isolation and characterization of charge-tagged phenylperoxyl radicals in the gas phase : direct evidence for products and pathways in low temperature benzene oxidation

Benjamin B. Kirk, David G. Harman, Hilkka I. Kenttamaa, Adam J. Trevitt, Stephen J. Blanksby

    Research output: Contribution to journalArticlepeer-review

    36 Citations (Scopus)

    Abstract

    The phenylperoxyl radical has long been accepted as a critical intermediate in the oxidation of benzene and an archetype for arylperoxyl radicals in combustion and atmospheric chemistry. Despite being central to many contemporary mechanisms underpinning these chemistries, reports of the direct detection or isolation of phenylperoxyl radicals are rare and there is little experimental evidence connecting this intermediate with expected product channels. We have prepared and isolated two charge-tagged phenyl radical models in the gas phase [i.e., 4-(N,N,N-trimethylammonium)phenyl radical cation and 4-carboxylatophenyl radical anion] and observed their reactions with dioxygen by ion-trap mass spectrometry. Measured reaction rates show good agreement with prior reports for the neutral system (k(2)[(Me(3)N(+))C(6)H(4).+ O(2)]=2.8X10(-11) cm(3) molecule(-1) s(-1), Φ = 4.9%; k(2)[((-)O(2)C)C(6)H(4).+ O(2)]=5.4X10(-11) cm(3) molecule(-1) s(-1), Φ = 9.2%) and the resulting mass spectra provide unequivocal evidence for the formation of phenylperoxyl radicals. Collisional activation of isolated phenylperoxyl radicals reveals unimolecular decomposition by three pathways: (i) loss of dioxygen to reform the initial phenyl radical; (ii) loss of atomic oxygen yielding a phenoxyl radical; and (iii) ejection of the formyl radical to give cyclopentadienone. Stable isotope labeling confirms these assignments. Quantum chemical calculations for both charge-tagged and neutral phenylperoxyl radicals confirm that loss of formyl radical is accessible both thermo-dynamically and entropically and competitive with direct loss of both hydrogen atom and carbon dioxide.
    Original languageEnglish
    Pages (from-to)16719-16730
    Number of pages12
    JournalPhysical Chemistry Chemical Physics
    Volume14
    Issue number48
    DOIs
    Publication statusPublished - 2012

    Fingerprint

    Dive into the research topics of 'Isolation and characterization of charge-tagged phenylperoxyl radicals in the gas phase : direct evidence for products and pathways in low temperature benzene oxidation'. Together they form a unique fingerprint.

    Cite this