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.; Ertl, M.; Fagnoni, M.; Knör, G; Ravelli, D.. - In: ACS CATALYSIS. - ISSN 2155-5435. - 10:(2020), pp. 9057-9064. [10.1021/acscatal.0c02250]

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

Capaldo L.;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
Antimony-Oxo Porphyrins as Photocatalysts for Redox-Neutral C–H to C–C Bond Conversion / Capaldo, L.; Ertl, M.; Fagnoni, M.; Knör, G; Ravelli, D.. - In: ACS CATALYSIS. - ISSN 2155-5435. - 10:(2020), pp. 9057-9064. [10.1021/acscatal.0c02250]
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11381/2961110
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