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    Reactions of a distonic peroxyl radical anion influenced by SOMO-HOMO conversion: an example of anion-directed channel switching

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    Author
    So, S; Kirk, BB; Wille, U; Trevitt, AJ; Blanksby, SJ; da Silva, G
    Date
    2020-01-28
    Source Title
    Physical Chemistry Chemical Physics
    Publisher
    Royal Society of Chemistry
    University of Melbourne Author/s
    da Silva, Gabriel; Wille, Uta; So, Sui
    Affiliation
    Chemical and Biomolecular Engineering
    School of Chemistry
    Biomedical Engineering
    Metadata
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    Document Type
    Journal Article
    Citations
    So, S., Kirk, B. B., Wille, U., Trevitt, A. J., Blanksby, S. J. & da Silva, G. (2020). Reactions of a distonic peroxyl radical anion influenced by SOMO-HOMO conversion: an example of anion-directed channel switching. Physical Chemistry Chemical Physics, 22 (4), pp.2130-2141. https://doi.org/10.1039/c9cp05989j.
    Access Status
    This item is currently not available from this repository
    URI
    http://hdl.handle.net/11343/252775
    DOI
    10.1039/c9cp05989j
    Abstract
    In free radicals the singly occupied molecular orbital (SOMO) typically has the highest energy. Recent examples of distonic radical anions were found, however, to disobey the usual orbital configuration, with the singly occupied molecular orbital buried energetically underneath doubly occupied orbitals. This unusual ordering of electrons, which contradicts the aufbau principle, has been characterized as SOMO–HOMO orbital conversion and is expected to perturb radical anion reactivity by branching toward anion-driven over radical-driven processes. Here, we use ion trap mass spectrometry and ab initio calculations to demonstrate that SOMO–HOMO orbital conversion influences the reactivity of a distonic peroxyl radical anion. Experimentally, we generated a distonic radical anion of β-hydroxy glutaric acid, ˙CH2CH(OH)CH2C(O)O−, and investigated its subsequent reaction with O2 in the gas phase. Theoretical calculations predict that reactions proceed through five isomeric C4H6O5˙− intermediates, two of which exhibit SOMO–HOMO conversion. The detected product ions, corresponding to loss of ˙OH + CO2, ˙OH + HCHO, HO2˙, and HO2˙ + CO2 from the peroxyl radical, can all be reconciled by the proposed reaction mechanism. Finally, we compare the oxygen recombination reaction of the distonic radical ion to the corresponding neutral radical (i.e., ˙CH2CH(OH)CH2C(O)OH). These calculations demonstrate that SOMO–HOMO conversion results in channel switching in the distonic radical anion, suppressing radical-driven mechanisms and promoting pathways that directly involve the anion site.

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