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

被引：33

作者：

Capaldo, Luca ^{[1
]}

Ertl, Martin ^{[2
]}

Fagnoni, Maurizio ^{[1
]}

Knoer, Guenther ^{[2
]}

Ravelli, Davide ^{[1
]}

机构：

[1] Univ Pavia, Dept Chem, PhotoGreen Lab, I-27100 Pavia, Italy

[2] Johannes Kepler Univ Linz JKU, Inst Inorgan Chem, A-4040 Linz, Austria

来源：

ACS CATALYSIS | 2020年 / 10卷 / 16期

关键词：

C-C bond formation; hydrogen atom transfer; photocatalysis; porphyrins; radical reactions; HYDROGEN-ATOM TRANSFER; VISIBLE-LIGHT; PHOTOCHEMICAL EPOXIDATION; MECHANISTIC INSIGHTS; CYCLOHEXENE; OXYGENATION; ACTIVATION; COMPLEXES; WATER; TETRAPHENYLPORPHYRINATOANTIMONY(V);

D O I：

10.1021/acscatal.0c02250

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

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.

引用

页码：9057 / 9064

页数：8

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