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Direct Detection of a Persistent Carbonyloxyl Radical in the Gas Phase

Authors

  • Dr. Berwyck L. J. Poad,

    Corresponding author
    1. School of Chemistry, University of Wollongong, NSW 2522 (Australia)
    • Berwyck L. J. Poad, School of Chemistry, University of Wollongong, NSW 2522 (Australia)

      Timothy Clark, Computer-Chemie-Centrum, Department Chemie und Parmazie, Friedrich-Alexander-University at Erlangen-Nürnberg, 91052 Erlangen (Germany)

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  • Dr. Benjamin B. Kirk,

    1. School of Chemistry, University of Wollongong, NSW 2522 (Australia)
    2. ARC Centre of Excellence for Free Radical Chemistry and Biotechnology, School of Chemistry, University of Wollongong, NSW 2522 (Australia)
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  • Pramesh I. Hettiarachchi,

    1. School of Chemistry, University of Wollongong, NSW 2522 (Australia)
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  • Dr. Adam J. Trevitt,

    1. School of Chemistry, University of Wollongong, NSW 2522 (Australia)
    2. ARC Centre of Excellence for Free Radical Chemistry and Biotechnology, School of Chemistry, University of Wollongong, NSW 2522 (Australia)
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  • Prof. Stephen J. Blanksby,

    1. School of Chemistry, University of Wollongong, NSW 2522 (Australia)
    2. ARC Centre of Excellence for Free Radical Chemistry and Biotechnology, School of Chemistry, University of Wollongong, NSW 2522 (Australia)
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  • Prof. Timothy Clark

    Corresponding author
    1. Computer-Chemie-Centrum, Department Chemie und Parmazie, Friedrich-Alexander-University at Erlangen-Nürnberg, 91052 Erlangen (Germany)
    2. Centre for Molecular Design, University of Portsmouth, King Henry Building, Portsmouth PO1 2DY (United Kingdom)
    • Berwyck L. J. Poad, School of Chemistry, University of Wollongong, NSW 2522 (Australia)

      Timothy Clark, Computer-Chemie-Centrum, Department Chemie und Parmazie, Friedrich-Alexander-University at Erlangen-Nürnberg, 91052 Erlangen (Germany)

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  • We acknowledge the financial support of the Australian Research Council (DP0986738, DP120102922, DE120100467) and the University of Wollongong. S.J.B., A.J.T., and B.B.K. acknowledge the support of the ARC Centre of Excellence for Free Radical Chemistry and Biotechnology (CE0561607). T.C. thanks the Excellence Cluster “Engineering of Advanced Materials”, funded by the Deutsche Forschungsgemeinschaft, for support. S.J.B. would like to acknowledge the helpful insights provided by the late Detlef Schröder following the initial presentation of our results at ASMS60 in Vancouver. Detlef’s generosity in sharing his passion for, and extraordinary insight into, the chemistry of gas-phase ions was an inspiration that will be sorely missed.

Abstract

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Long lived: Carbonyloxyl radicals (RCO2.) are reactive intermediates that play key roles in initiating polymerization reactions. This reactivity also makes their direct observation difficult. For the first time a persistent organic RCO2. radical is detected in the gas phase, its extraordinary longevity is attributed to the high barrier towards fragmentation owing to the endothermicity of the decarboxylation products.

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