title: Bottom-Up Construction of a CO2-Based Cycle for the Photocarbonylation of Benzene, Promoted by a Rhodium(I) Pincer Complex.
abstract: 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.
authors.affiliation: Departments of †Organic Chemistry and ‡Chemical Research Support, Weizmann Institute of Science , Rehovot 76100, Israel.
authors.forename: Aviel
authors.initials: A
authors.lastname: Anaby
authors.affiliation: Departments of †Organic Chemistry and ‡Chemical Research Support, Weizmann Institute of Science , Rehovot 76100, Israel.
authors.forename: Moran
authors.initials: M
authors.lastname: Feller
authors.affiliation: Departments of †Organic Chemistry and ‡Chemical Research Support, Weizmann Institute of Science , Rehovot 76100, Israel.
authors.forename: Yehoshoa
authors.initials: Y
authors.lastname: Ben-David
authors.affiliation: Departments of †Organic Chemistry and ‡Chemical Research Support, Weizmann Institute of Science , Rehovot 76100, Israel.
authors.forename: Gregory
authors.initials: G
authors.lastname: Leitus
authors.affiliation: Departments of †Organic Chemistry and ‡Chemical Research Support, Weizmann Institute of Science , Rehovot 76100, Israel.
authors.forename: Yael
authors.initials: Y
authors.lastname: Diskin-Posner
authors.affiliation: Departments of †Organic Chemistry and ‡Chemical Research Support, Weizmann Institute of Science , Rehovot 76100, Israel.
authors.forename: Linda J W
authors.initials: LJ
authors.lastname: Shimon
authors.affiliation: Departments of †Organic Chemistry and ‡Chemical Research Support, Weizmann Institute of Science , Rehovot 76100, Israel.
authors.forename: David
authors.initials: D
authors.lastname: Milstein