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Updated: May 15, 2025

Photogeneration of N-Heterocyclic Carbenes: Application in Photoinduced Ring-Opening Metathesis Polymerization
Published on: November 29, 2018
Ligand-Enabled Photoinduced Ruthenium Catalysis for Ortho-C─O Bond Formation at Room Temperature
Chandrasekaran Sivaraj1, Ajay Thonipalliyalil Udayan1, Karthick Muthuvel1
1Department of Chemistry, Vellore Institute of Technology, Vellore, Tamil Nadu, India.
Abstract:
Photoinduced ruthenium-catalyzed ortho-benzoxylation through organophosphine ligand is unveiled. The in situ generation of the organophosphine-ruthenium complex facilitates ligand-to-metal charge transfer (LMCT) under visible light, promoting the site-selective ortho-benzoxylation at room temperature. The broad scope of aryl, aliphatic, and heterocyclic carboxylic acids are key attractions of this methodology. EPR and UV-Vis analysis support a LMCT process between a photoexcited organophosphine and Ru-complex under blue-light irradiation. Comprehensive mechanistic investigation highlights the role of light, ligands, oxidants, the LMCT process, and the unique reactivity of the directing group.
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