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Antimony–Oxo Porphyrins as Photocatalysts for Redox-Neutral C–H to C–C Bond Conversion
[Image: see text] The use of high-valent antimony–oxo porphyrins as visible-light photocatalysts operating via direct hydrogen atom transfer has been demonstrated. Computational analysis indicates that the triplet excited state of these complexes shows an oxyl radical behavior, while the Sb(V) cente...
Autores principales: | , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
American
Chemical Society
2020
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Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8009479/ https://www.ncbi.nlm.nih.gov/pubmed/33815891 http://dx.doi.org/10.1021/acscatal.0c02250 |
Sumario: | [Image: see text] The use of high-valent antimony–oxo porphyrins as visible-light photocatalysts operating via direct hydrogen atom transfer has been demonstrated. Computational analysis indicates that the triplet excited state of these complexes shows an oxyl radical behavior, while the Sb(V) center remains in a high-valent oxidation state, serving uniquely to carry the oxo moiety and activate the coordinated ligands. This porphyrin-based system has been exploited upon irradiation to catalyze C–H to C–C bond conversion via the addition of hydrogen donors (ethers and aldehydes) onto Michael acceptors in a redox-neutral fashion without the need of any external oxidant. Laser flash photolysis experiments confirmed that the triplet excited state of the photocatalyst triggers the desired C–H cleavage. |
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