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

Aviel Anaby, Moran Feller, Yehoshoa Ben-David, Gregory Leitus, Yael Diskin-Posner, Linda J W Shimon, David Milstein

Research output: Contribution to journalArticle

17 Citations (Scopus)

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.

Original languageEnglish
Pages (from-to)9941-9950
Number of pages10
JournalJournal of the American Chemical Society
Volume138
Issue number31
DOIs
Publication statusPublished - Aug 10 2016

Fingerprint

Rhodium
Benzene
Hydrides
Metals
X ray crystallography
X Ray Crystallography
Organometallics
Catalysis
Carbon Dioxide
Feedstocks
Nuclear magnetic resonance spectroscopy
Carbon dioxide
Magnetic Resonance Spectroscopy
Chemical activation
Ligands

ASJC Scopus subject areas

  • Catalysis
  • Biochemistry
  • Chemistry(all)
  • Colloid and Surface Chemistry

Cite this

Bottom-Up Construction of a CO2-Based Cycle for the Photocarbonylation of Benzene, Promoted by a Rhodium(I) Pincer Complex. / Anaby, Aviel; Feller, Moran; Ben-David, Yehoshoa; Leitus, Gregory; Diskin-Posner, Yael; Shimon, Linda J W; Milstein, David.

In: Journal of the American Chemical Society, Vol. 138, No. 31, 10.08.2016, p. 9941-9950.

Research output: Contribution to journalArticle

Anaby, Aviel ; Feller, Moran ; Ben-David, Yehoshoa ; Leitus, Gregory ; Diskin-Posner, Yael ; Shimon, Linda J W ; Milstein, David. / Bottom-Up Construction of a CO2-Based Cycle for the Photocarbonylation of Benzene, Promoted by a Rhodium(I) Pincer Complex. In: Journal of the American Chemical Society. 2016 ; Vol. 138, No. 31. pp. 9941-9950.
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