Abstract

Seven ruthenium catalysts with the general formula [(CNC)Ru(CH3CN)2Cl]OTf have been used to understand structure function relationships in the sensitized photocatalytic CO2 reduction reaction. Herein, CNC is a pincer ligand containing imidazole‐based N‐heterocyclic carbenes (NHCs) attached to a central pyridyl ring with R groups at the 3‐ or 4‐position. Two new complexes (R = 3‐OMe, 4‐NPh2) have been fully characterized by analytical and spectroscopic methods and single‐crystal X‐ray diffraction. Furthermore, three previously synthesized complexes (R = 4‐Me, 4‐NMe2, and 4‐OH) are used for photocatalysis for the first time. Methoxy and methyl donor groups in the 4‐position lead to durable catalysts (TON up to 1000) with high TOFs (up to 174 h–1) for CO production. In contrast, R = 4‐NPh2, 3‐OMe, and 4‐H substituents lead to modest TOF values (up to 32 h–1), yet these systems are still robust and achieve up to 565 TON. In contrast, low activity is observed with 4‐NMe2 and 4‐OH substituents, which resemble sacrificial donors and may be leading to side reactions. Thus, remote substituents were found to greatly influence catalyst activity and longevity.

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