A journey into metal–carbon bond homolysis
This article surveys the current knowledge in metal alkyl complexes with homolytically weak metal–carbon bonds, therefore prone to thermally produce alkyl radicals. It outlines the role of a metal complex as a moderator to control the radical reactivity (“persistent radical effect”). It describes th...
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| Format: | Article |
| Language: | English |
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Académie des sciences
2021-04-01
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| Series: | Comptes Rendus. Chimie |
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| Online Access: | https://comptes-rendus.academie-sciences.fr/chimie/articles/10.5802/crchim.73/ |
| _version_ | 1797651406712209408 |
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| author | Poli, Rinaldo |
| author_facet | Poli, Rinaldo |
| author_sort | Poli, Rinaldo |
| collection | DOAJ |
| description | This article surveys the current knowledge in metal alkyl complexes with homolytically weak metal–carbon bonds, therefore prone to thermally produce alkyl radicals. It outlines the role of a metal complex as a moderator to control the radical reactivity (“persistent radical effect”). It describes the methods that have been used so far (as well as others that are potentially available) to investigate the metal–carbon bond cleavage thermodynamic and kinetic parameters, including their caveats and limitations. A number of systems scrutinized in the author’s own laboratory and in those of collaborators are presented and discussed. These investigations have combined metal complexes and alkyl radicals, with guidance and understanding provided by DFT calculations, to achieve higher performance in the controlled radical polymerization of challenging monomers (vinyl acetate, vinylidene fluoride) and in olefin radical cross-coupling, and have brought to light mechanistic questions of more general relevance. |
| first_indexed | 2024-03-11T16:14:34Z |
| format | Article |
| id | doaj.art-c0ce49587629456bb5fe4e5840cf3a23 |
| institution | Directory Open Access Journal |
| issn | 1878-1543 |
| language | English |
| last_indexed | 2024-03-11T16:14:34Z |
| publishDate | 2021-04-01 |
| publisher | Académie des sciences |
| record_format | Article |
| series | Comptes Rendus. Chimie |
| spelling | doaj.art-c0ce49587629456bb5fe4e5840cf3a232023-10-24T14:22:53ZengAcadémie des sciencesComptes Rendus. Chimie1878-15432021-04-0124114717510.5802/crchim.7310.5802/crchim.73A journey into metal–carbon bond homolysisPoli, Rinaldo0https://orcid.org/0000-0002-5220-2515Laboratoire de Chimie de Coordination, 205 Route de Narbonne, 31077 Toulouse, FranceThis article surveys the current knowledge in metal alkyl complexes with homolytically weak metal–carbon bonds, therefore prone to thermally produce alkyl radicals. It outlines the role of a metal complex as a moderator to control the radical reactivity (“persistent radical effect”). It describes the methods that have been used so far (as well as others that are potentially available) to investigate the metal–carbon bond cleavage thermodynamic and kinetic parameters, including their caveats and limitations. A number of systems scrutinized in the author’s own laboratory and in those of collaborators are presented and discussed. These investigations have combined metal complexes and alkyl radicals, with guidance and understanding provided by DFT calculations, to achieve higher performance in the controlled radical polymerization of challenging monomers (vinyl acetate, vinylidene fluoride) and in olefin radical cross-coupling, and have brought to light mechanistic questions of more general relevance.https://comptes-rendus.academie-sciences.fr/chimie/articles/10.5802/crchim.73/Metal–carbon bondHomolytic cleavageBond dissociation enthalpyPersistent radical effectMetal-mediated radical reactivity |
| spellingShingle | Poli, Rinaldo A journey into metal–carbon bond homolysis Comptes Rendus. Chimie Metal–carbon bond Homolytic cleavage Bond dissociation enthalpy Persistent radical effect Metal-mediated radical reactivity |
| title | A journey into metal–carbon bond homolysis |
| title_full | A journey into metal–carbon bond homolysis |
| title_fullStr | A journey into metal–carbon bond homolysis |
| title_full_unstemmed | A journey into metal–carbon bond homolysis |
| title_short | A journey into metal–carbon bond homolysis |
| title_sort | journey into metal carbon bond homolysis |
| topic | Metal–carbon bond Homolytic cleavage Bond dissociation enthalpy Persistent radical effect Metal-mediated radical reactivity |
| url | https://comptes-rendus.academie-sciences.fr/chimie/articles/10.5802/crchim.73/ |
| work_keys_str_mv | AT polirinaldo ajourneyintometalcarbonbondhomolysis AT polirinaldo journeyintometalcarbonbondhomolysis |