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

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• 作者：Aviel Anaby ; Moran Feller ; Yehoshoa Ben-David ; Gregory Leitus ; Yael Diskin-Posner ; Linda J. W. Shimon ; David Milstein
• 刊名：Journal of the American Chemical Society
• 出版年：2016
• 出版时间：August 10, 2016
• 年：2016
• 卷：138
• 期：31
• 页码：9941-9950
• 全文大小：590K
• 年卷期：0
• ISSN：1520-5126

文摘

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.