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    Effect of Chemical Structure on the Electrochemical Cleavage of Alkoxyamines

    80772.pdf (1.707Mb)
    Access Status
    Open access
    Authors
    Hammill, C.L.
    Noble, B.B.
    Norcott, P.L.
    Ciampi, Simone
    Coote, M.L.
    Date
    2019
    Type
    Journal Article
    
    Metadata
    Show full item record
    Citation
    Hammill, C.L. and Noble, B.B. and Norcott, P.L. and Ciampi, S. and Coote, M.L. 2019. Effect of Chemical Structure on the Electrochemical Cleavage of Alkoxyamines. Journal of Physical Chemistry C. 123 (9): pp. 5273-5281.
    Source Title
    Journal of Physical Chemistry C
    DOI
    10.1021/acs.jpcc.8b12545
    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/FL170100041
    http://purl.org/au-research/grants/arc/DE160100732
    http://purl.org/au-research/grants/arc/CE140100012
    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.8b12545.

    URI
    http://hdl.handle.net/20.500.11937/80753
    Collection
    • Curtin Research Publications
    Abstract

    A test set of 14 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO)-based alkoxyamines was studied via a combination of cyclic voltammetry and accurate quantum chemistry to assess the effect of substituents on electrochemical cleavage. The experimental oxidation potentials of alkoxyamines falling into the range of 1.1-1.6 V versus Ag/AgCl in acetonitrile, were well reproduced by theory (MAD 0.04 V), with values showing good correlation with the σR Hammett parameters of both the R-group and the OR-group in TEMPO-R. Importantly, most of the studied alkoxyamines underwent oxidative cleavage to form either TEMPO· and R+ or TEMPO+ and R·, with the former favored by electron-donating substituents on R (e.g., 2-oxolane, Ac, CH(CH3)Ph, i-Pr, t-Bu) and the latter by electron withdrawing substituents (Bn, allyl, CH(CH3)C(O)OCH3, C(CH3)2C(O)OCH3, CH(CH3)CN). Where R is not stabilized (e.g., R = CH2C(O)OCH3, Me, Et), fully or almost fully reversible oxidation - without cleavage - was observed, making these species promising candidates for battery applications. Finally, in the case of R = Ph, where N-O cleavage occurred, a phenoxy cation and an aminyl radical were generated. On the basis of these results, TEMPO-based alkoxyamines can provide a variety of electrochemically generated carbon-centered radicals and carbocations for use in synthesis, polymerization, and surface modification.

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