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    Mechanism of Oxidative Alkoxyamine Cleavage: The Surprising Role of the Solvent and Supporting Electrolyte

    80771.pdf (1.625Mb)
    Access Status
    Open access
    Authors
    Noble, B.B.
    Norcott, P.L.
    Hammill, C.L.
    Ciampi, Simone
    Coote, M.L.
    Date
    2019
    Type
    Journal Article
    
    Metadata
    Show full item record
    Citation
    Noble, B.B. and Norcott, P.L. and Hammill, C.L. and Ciampi, S. and Coote, M.L. 2019. Mechanism of Oxidative Alkoxyamine Cleavage: The Surprising Role of the Solvent and Supporting Electrolyte. Journal of Physical Chemistry C. 123 (16): pp. 10300-10305.
    Source Title
    Journal of Physical Chemistry C
    DOI
    10.1021/acs.jpcc.9b01832
    ISSN
    1932-7447
    Faculty
    Faculty of Science and Engineering
    School
    School of Molecular and Life Sciences (MLS)
    Funding and Sponsorship
    http://purl.org/au-research/grants/arc/CE140100012
    http://purl.org/au-research/grants/arc/FL170100041
    http://purl.org/au-research/grants/arc/DE160100732
    Remarks

    This document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of Physical Chemistry C, copyright © American Chemical Society, after peer review and technical editing by the publisher. To access the final edited and published work seehttps://doi.org/10.1021/acs.jpcc.9b01832.

    URI
    http://hdl.handle.net/20.500.11937/80752
    Collection
    • Curtin Research Publications
    Abstract

    In this work, we show that the nature of the supporting electrolyte and solvent can dramatically alter the outcome of the electrochemically mediated cleavage of alkoxyamines. A combination of cyclic voltammetry experiments and quantum chemistry is used to study the oxidation behavior of TEMPO-i-Pr under different conditions. In dichloromethane, using a noncoordinating electrolyte (TBAPF6), TEMPO-i-Pr undergoes reversible oxidation, which indicates that the intermediate radical cation is stable toward mesolytic fragmentation. In contrast, in tetrahydrofuran with the same electrolyte, oxidized TEMPO-i-Pr undergoes a rapid and irreversible fragmentation. In nitromethane and acetonitrile, partially irreversible oxidation is observed, indicating that fragmentation is much slower. Likewise, alkoxyamine oxidation in the presence of more strongly coordinating supporting electrolyte anions (BF4-, ClO4-, OTf-, HSO4-, NO3-) is also irreversible. These observations can be explained in terms of solvent- or electrolyte-mediated SN2 pathways and indicate that oxidative alkoxyamine cleavage can be "activated" by introducing coordinating solvents or electrolytes or be "inhibited" through the use of noncoordinating solvents and electrolytes.

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