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Smart Control of Nitroxide-Mediated Polymerization Initiators’ Reactivity by pH, Complexation with Metals, and Chemical Transformations

1
N. N. Vorozhtsov Institute of Organic Chemistry SB RAS, Pr. Lavrentjeva 9, Novosibirsk 630090, Russia
2
National Research University—Novosibirsk State University, Novosibirsk 630090, Russia
3
Aix Marseille Univ, CNRS, ICR, UMR 7273, case 551, Avenue Escadrille Normandie-Niemen, 13397 Marseille CEDEX 20, France
*
Author to whom correspondence should be addressed.
Materials 2019, 12(5), 688; https://doi.org/10.3390/ma12050688
Received: 24 January 2019 / Revised: 15 February 2019 / Accepted: 20 February 2019 / Published: 26 February 2019
(This article belongs to the Special Issue Novel Materials and Applications by Controlled Radical Polymerization)
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PDF [4345 KB, uploaded 26 February 2019]
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Abstract

Because alkoxyamines are employed in a number of important applications, such as nitroxide-mediated polymerization, radical chemistry, redox chemistry, and catalysis, research into their reactivity is especially important. Typically, the rate of alkoxyamine homolysis is strongly dependent on temperature. Nonetheless, thermal regulation of such reactions is not always optimal. This review describes various ways to reversibly change the rate of C–ON bond homolysis of alkoxyamines at constant temperature. The major methods influencing C–ON bond homolysis without alteration of temperature are protonation of functional groups in an alkoxyamine, formation of metal–alkoxyamine complexes, and chemical transformation of alkoxyamines. Depending on the structure of an alkoxyamine, these approaches can have a significant effect on the homolysis rate constant, by a factor of up to 30, and can shorten the half-lifetime from days to seconds. These methods open new prospects for the application of alkoxyamines in biology and increase the safety of (and control over) the nitroxide-mediated polymerization method. View Full-Text
Keywords: nitroxide mediated polymerization; alkoxyamine; tunable rate constants; protonation; complexation nitroxide mediated polymerization; alkoxyamine; tunable rate constants; protonation; complexation
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This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited (CC BY 4.0).
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Edeleva, M.; Audran, G.; Marque, S.; Bagryanskaya, E. Smart Control of Nitroxide-Mediated Polymerization Initiators’ Reactivity by pH, Complexation with Metals, and Chemical Transformations. Materials 2019, 12, 688.

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