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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 SbV 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.

Antimony-Oxo Porphyrins as Photocatalysts for Redox-Neutral C–H to C–C Bond Conversion

Capaldo L.;Fagnoni M.;Ravelli D.
2020-01-01

Abstract

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 SbV 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.
2020
The Organic Chemistry/Polymer Science category includes resources concerned with the related fields of organic chemistry and polymer science. The organic chemistry resources deal with compounds of carbon with the exception of certain simple ones, such as the carbon oxides, carbonates, cyanides and cyanates (see Inorganic & Nuclear Chemistry). This category includes research on synthetic and natural organic compounds that may include other elements, such as hydrogen and oxygen, but also nitrogen, halogens, sulphur and phosphorous. Resources concerned with hydrocarbons, organic compounds containing only the elements carbon and hydrogen, are also included in this category. Examples are the alkanes, alkenes, alkynes and aromatics, such as benzene and naphthalene. Polymer science includes all resources dealing with the study, production and technology of polymers, which are compounds composed of very large molecules made up of repeating molecular units (monomers). Polymers may be natural substances, such as polysaccharides or proteins, or synthetic materials, such as nylon or polyethylene.
ACS CATALYSIS
sì
WOS:000563749900008
2-s2.0-85091832934
Esperti anonimi
Inglese
Internazionale
ELETTRONICO
10
9057
9064
8
C−C bond formation, hydrogen atom transfer, photocatalysis, porphyrins, radical reactions
https://dx.doi.org/10.1021/acscatal.0c02250
sì
5
info:eu-repo/semantics/article
262
Capaldo, L.; Ertl, M.; Fagnoni, M.; Knör, G; Ravelli, D.
1 Contributo su Rivista::1.1 Articolo in rivista
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1.1 Articolo in rivista
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11571/1347075
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