4.6 Article

New Co and Mn Catalysts Bearing ONO Ligands Containing Nucleophile for the Coupling of CO2 and Propylene Oxide

Journal

CATALYSTS
Volume 12, Issue 11, Pages -

Publisher

MDPI
DOI: 10.3390/catal12111443

Keywords

carbon dioxide; CO2 utilization; homogeneous catalysis; cyclic carbonates; ONO ligands; CO2 coupling reactions; ionic pendant-armed ligands; manganese catalysts; cobalt catalysts

Funding

  1. Repsol
  2. Eurecat [TQC16006S, TQC14029S]
  3. Spanish Ministerio de Economia y Competitividad [CTQ2016-75016-R, 2017 SGR 1472]
  4. Instituto Valenciano de Competitividad Empresarial (IVACE) in the Comunitat Valenciana [IMAMCA/2022/4]

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A series of novel ONO ligands with an ionic pendant-armed were successfully synthesized and coordinated to cobalt and manganese precursors. Among these, the manganese complex showed the best catalytic activity towards the formation of propylene carbonate.
A series of novel ONO ligands bearing an ionic pendant-armed (hereinafter indicated as ONONu, where Nu corresponds to an anionic nucleophile) were synthesized, characterized, and successfully coordinated to cobalt and manganese precursors. New air-stable cobalt (III) complexes (1-6) and manganese (II) complexes (7 and 8) were obtained and characterized. Single crystal X-ray diffraction analysis of the Co(III) compound 5 confirmed the presence of two quaternized ligands coordinated to the metal and iodide as counterion. These novel complexes were revealed to be active catalysts in the coupling reaction of carbon dioxide and propylene oxide (PO) in different degrees of success. Among these, the manganese complex 8 afforded the best results towards the formation of propylene carbonate (PC) with a productivity of 256 kg PC/(kg cat center dot h), achieving a TON of 4860.

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