Smart Control of Nitroxide-Mediated Polymerization Initiators’ Reactivity by pH, Complexation with Metals, and Chemical Transformations
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 tempera...
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| Format: | Article |
| Language: | English |
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MDPI AG
2019-02-01
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| Series: | Materials |
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| Online Access: | https://www.mdpi.com/1996-1944/12/5/688 |
| _version_ | 1811269854043308032 |
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| author | Mariya Edeleva Gerard Audran Sylvain Marque Elena Bagryanskaya |
| author_facet | Mariya Edeleva Gerard Audran Sylvain Marque Elena Bagryanskaya |
| author_sort | Mariya Edeleva |
| collection | DOAJ |
| description | 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. |
| first_indexed | 2024-04-12T21:50:32Z |
| format | Article |
| id | doaj.art-2b5f716e48bf436b97db6637989a3063 |
| institution | Directory Open Access Journal |
| issn | 1996-1944 |
| language | English |
| last_indexed | 2024-04-12T21:50:32Z |
| publishDate | 2019-02-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Materials |
| spelling | doaj.art-2b5f716e48bf436b97db6637989a30632022-12-22T03:15:30ZengMDPI AGMaterials1996-19442019-02-0112568810.3390/ma12050688ma12050688Smart Control of Nitroxide-Mediated Polymerization Initiators’ Reactivity by pH, Complexation with Metals, and Chemical TransformationsMariya Edeleva0Gerard Audran1Sylvain Marque2Elena Bagryanskaya3N. N. Vorozhtsov Institute of Organic Chemistry SB RAS, Pr. Lavrentjeva 9, Novosibirsk 630090, RussiaAix Marseille Univ, CNRS, ICR, UMR 7273, case 551, Avenue Escadrille Normandie-Niemen, 13397 Marseille CEDEX 20, FranceAix Marseille Univ, CNRS, ICR, UMR 7273, case 551, Avenue Escadrille Normandie-Niemen, 13397 Marseille CEDEX 20, FranceN. N. Vorozhtsov Institute of Organic Chemistry SB RAS, Pr. Lavrentjeva 9, Novosibirsk 630090, RussiaBecause 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.https://www.mdpi.com/1996-1944/12/5/688nitroxide mediated polymerizationalkoxyaminetunable rate constantsprotonationcomplexation |
| spellingShingle | Mariya Edeleva Gerard Audran Sylvain Marque Elena Bagryanskaya Smart Control of Nitroxide-Mediated Polymerization Initiators’ Reactivity by pH, Complexation with Metals, and Chemical Transformations Materials nitroxide mediated polymerization alkoxyamine tunable rate constants protonation complexation |
| title | Smart Control of Nitroxide-Mediated Polymerization Initiators’ Reactivity by pH, Complexation with Metals, and Chemical Transformations |
| title_full | Smart Control of Nitroxide-Mediated Polymerization Initiators’ Reactivity by pH, Complexation with Metals, and Chemical Transformations |
| title_fullStr | Smart Control of Nitroxide-Mediated Polymerization Initiators’ Reactivity by pH, Complexation with Metals, and Chemical Transformations |
| title_full_unstemmed | Smart Control of Nitroxide-Mediated Polymerization Initiators’ Reactivity by pH, Complexation with Metals, and Chemical Transformations |
| title_short | Smart Control of Nitroxide-Mediated Polymerization Initiators’ Reactivity by pH, Complexation with Metals, and Chemical Transformations |
| title_sort | smart control of nitroxide mediated polymerization initiators reactivity by ph complexation with metals and chemical transformations |
| topic | nitroxide mediated polymerization alkoxyamine tunable rate constants protonation complexation |
| url | https://www.mdpi.com/1996-1944/12/5/688 |
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