In this manuscript, a photoinduced ligand-to-metal charge transfer (LMCT) approach, employing transition-metal-based photocatalysts, for the efficient alkylation of electron-poor olefin is described. The developed redox-neutral process benefits from mild reaction conditions and involves a wide range of chromone-3-carboxylic acids as well as nucleophiles amenable to selective C-H functionalization leading to the formation of 2-substituted chroman-4-one compounds with potential biological activity.
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http://dx.doi.org/10.1039/d3cc05331h | DOI Listing |
J Am Chem Soc
December 2024
Department of Chemistry, Princeton University, Princeton, New Jersey 08544, United States.
Photoinduced ligand-to-metal charge transfer (LMCT) is a powerful technique for the formation of reactive radical species via homolytic cleavage of the metal-ligand bond. Here, we present that the excited state LMCT of a cobyrinate complex can be accessed by tuning its axial coordination with thiolates as ligands. We demonstrate the photoreduction of cobalt via the excited state Co-S bond homolytic cleavage, as guided by the DFT calculations, which signify the relevance of thiolate axial ligands facilitating the LMCT reactivity.
View Article and Find Full Text PDFJ Org Chem
December 2024
Green Pharmaceutical Technology Key Laboratory of Luzhou City, School of Pharmacy, Southwest Medical University, Luzhou, Sichuan 646000, P. R. China.
A cerium-catalyzed C-H alkylation of -sulfonyl ketimines with low-cost and readily available alkanes as alkyl sources was developed. This transformation proceeded through the synergy of photoinitiated ligand-to-metal charge transfer (LMCT) using a chlorine radical as an HAT reagent and air as a green oxidant. A series of alkylated -sulfonyl ketimines were synthesized with moderate to good yields in a highly atom-economic manner under chemical oxidant-free conditions.
View Article and Find Full Text PDFJ Hazard Mater
November 2024
State Key Lab of Geohazard prevention & Geoenvironment protection, College of Materials and Chemistry & Chemical Engineering, Chengdu University of Technology, Chengdu 610059, China. Electronic address:
J Phys Chem C Nanomater Interfaces
October 2024
Department of Chemistry, University of Kentucky, Lexington, Kentucky 40506, United States.
Semiconductor photocatalysis with commercial TiO (Degussa P25) has shown significant potential in water treatment of organic pollutants. However, the photoinduced reactions of adsorbed catechol, a phenolic air pollutant from biomass burning and combustion emissions, at the air-solid interface of TiO remain unexplored. Herein we examine the photocatalytic decay of catechol in the presence of water vapor, which acts as an electron acceptor.
View Article and Find Full Text PDFInorg Chem
October 2024
KAUST Catalysis Center (KCC), King Abdullah University of Science and Technology (KAUST), Thuwal 23955-6900, Saudi Arabia.
The mechanism of visible light-driven Ni-C(aryl) bond homolysis in (2,2'-bipyridine)Ni(aryl)(halide) complexes, which play a crucial role in metallaphotoredox catalysis for cross-coupling reactions, has been well studied. Differently, the theoretical understanding of Ni-halide bond homolysis remains limited. In this study, we introduce a novel electronic structural framework to elucidate the mechanisms underlying photoinduced Ni-Br bond rupture in the (dtbbpy)Ni(aryl)(Br) complex.
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