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How intramolecular coordination bonding (ICB) controls the homolysis of the C–ON bond in alkoxyamines

Because the C–ON bond homolysis rate constant k(d) is an essential parameter of alkoxyamine reactivity, it is especially important to tune k(d) without a major alteration of the structure of the molecule. Recently, several approaches have become known, e.g., protonation of functional groups and form...

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Autores principales: Audran, Gérard, Bagryanskaya, Elena, Bagryanskaya, Irina, Edeleva, Mariya, Joly, Jean-Patrick, Marque, Sylvain R. A., Iurchenkova, Anna, Kaletina, Polina, Cherkasov, Sergey, Hai, Tung To, Tretyakov, Evgeny, Zhivetyeva, Svetlana
Formato: Online Artículo Texto
Lenguaje:English
Publicado: The Royal Society of Chemistry 2019
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9070044/
https://www.ncbi.nlm.nih.gov/pubmed/35530086
http://dx.doi.org/10.1039/c9ra05334d
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author Audran, Gérard
Bagryanskaya, Elena
Bagryanskaya, Irina
Edeleva, Mariya
Joly, Jean-Patrick
Marque, Sylvain R. A.
Iurchenkova, Anna
Kaletina, Polina
Cherkasov, Sergey
Hai, Tung To
Tretyakov, Evgeny
Zhivetyeva, Svetlana
author_facet Audran, Gérard
Bagryanskaya, Elena
Bagryanskaya, Irina
Edeleva, Mariya
Joly, Jean-Patrick
Marque, Sylvain R. A.
Iurchenkova, Anna
Kaletina, Polina
Cherkasov, Sergey
Hai, Tung To
Tretyakov, Evgeny
Zhivetyeva, Svetlana
author_sort Audran, Gérard
collection PubMed
description Because the C–ON bond homolysis rate constant k(d) is an essential parameter of alkoxyamine reactivity, it is especially important to tune k(d) without a major alteration of the structure of the molecule. Recently, several approaches have become known, e.g., protonation of functional groups and formation of metal complexes. In this paper, coordination reactions of [Zn(hfac)(2)(H(2)O)(2)] with a series of new SG1-based alkoxyamines affording complexes with different structures are presented. The k(d) values of the complexed forms of the alkoxyamines were compared to those of free and protonated ones to reveal the contribution of the electron-withdrawing property and structure stabilization. Together with previously published data, this work provides clues to the design of alkoxyamines that can be effectively activated upon coordination with metal ions. Furthermore, our results provide insight into the mechanism underlying the influence of complexation on the reactivity of alkoxyamines. This led us to describe different types of coordination: intramolecular in nitroxyl fragment, intramolecular in alkyl fragment, intramolecular between alkyl and nitroxyl fragment, and intermolecular one. All of them exhibit different trends which are dramatically altered by changes in conformation.
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spelling pubmed-90700442022-05-05 How intramolecular coordination bonding (ICB) controls the homolysis of the C–ON bond in alkoxyamines Audran, Gérard Bagryanskaya, Elena Bagryanskaya, Irina Edeleva, Mariya Joly, Jean-Patrick Marque, Sylvain R. A. Iurchenkova, Anna Kaletina, Polina Cherkasov, Sergey Hai, Tung To Tretyakov, Evgeny Zhivetyeva, Svetlana RSC Adv Chemistry Because the C–ON bond homolysis rate constant k(d) is an essential parameter of alkoxyamine reactivity, it is especially important to tune k(d) without a major alteration of the structure of the molecule. Recently, several approaches have become known, e.g., protonation of functional groups and formation of metal complexes. In this paper, coordination reactions of [Zn(hfac)(2)(H(2)O)(2)] with a series of new SG1-based alkoxyamines affording complexes with different structures are presented. The k(d) values of the complexed forms of the alkoxyamines were compared to those of free and protonated ones to reveal the contribution of the electron-withdrawing property and structure stabilization. Together with previously published data, this work provides clues to the design of alkoxyamines that can be effectively activated upon coordination with metal ions. Furthermore, our results provide insight into the mechanism underlying the influence of complexation on the reactivity of alkoxyamines. This led us to describe different types of coordination: intramolecular in nitroxyl fragment, intramolecular in alkyl fragment, intramolecular between alkyl and nitroxyl fragment, and intermolecular one. All of them exhibit different trends which are dramatically altered by changes in conformation. The Royal Society of Chemistry 2019-08-16 /pmc/articles/PMC9070044/ /pubmed/35530086 http://dx.doi.org/10.1039/c9ra05334d Text en This journal is © The Royal Society of Chemistry https://creativecommons.org/licenses/by-nc/3.0/
spellingShingle Chemistry
Audran, Gérard
Bagryanskaya, Elena
Bagryanskaya, Irina
Edeleva, Mariya
Joly, Jean-Patrick
Marque, Sylvain R. A.
Iurchenkova, Anna
Kaletina, Polina
Cherkasov, Sergey
Hai, Tung To
Tretyakov, Evgeny
Zhivetyeva, Svetlana
How intramolecular coordination bonding (ICB) controls the homolysis of the C–ON bond in alkoxyamines
title How intramolecular coordination bonding (ICB) controls the homolysis of the C–ON bond in alkoxyamines
title_full How intramolecular coordination bonding (ICB) controls the homolysis of the C–ON bond in alkoxyamines
title_fullStr How intramolecular coordination bonding (ICB) controls the homolysis of the C–ON bond in alkoxyamines
title_full_unstemmed How intramolecular coordination bonding (ICB) controls the homolysis of the C–ON bond in alkoxyamines
title_short How intramolecular coordination bonding (ICB) controls the homolysis of the C–ON bond in alkoxyamines
title_sort how intramolecular coordination bonding (icb) controls the homolysis of the c–on bond in alkoxyamines
topic Chemistry
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9070044/
https://www.ncbi.nlm.nih.gov/pubmed/35530086
http://dx.doi.org/10.1039/c9ra05334d
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