Bottom-Up Construction of a CO₂‑Based Cycle for the Photocarbonylation of Benzene, Promoted by a Rhodium(I) Pincer Complex

The use of carbon dioxide for synthetic applications presents a major goal in modern homogeneous catalysis. Rhodium–hydride PNP pincer complex 1 is shown to add CO₂ in two disparate pathways: one is the expected insertion of CO₂ into the metal–hydride bond, and the other leads to reductive cleavage of CO₂, involving metal–ligand cooperation. The resultant rhodium–carbonyl complex was found to be photoactive, enabling the activation of benzene and formation of a new benzoyl complex. Organometallic intermediate species were observed and characterized by NMR spectroscopy and X-ray crystallography. Based on the series of individual transformations, a sequence for the photocarbonylation of benzene using CO₂ as the feedstock was constructed and demonstrated for the production of benzaldehyde from benzene.