Selective reduction and homologation of carbon monoxide by organometallic iron complexes

Sharpe, Helen R.; Geer, Ana M.; Taylor, Laurence J.; Gridley, Benjamin M.; Blundell, Toby J.; Blake, Alexander J.; Davies, E. Stephen; Lewis, William; McMaster, Jonathan; Robinson, David; Kays, Deborah L.

Abstract

Carbon monoxide is a key C1 feedstock for the industrial production of hydrocarbons, where it is used to make millions of tonnes of chemicals, fuels, and solvents per annum. Many transition metal complexes can coordinate CO2 but the formation of new C―C bonds in well- defined compounds from the scission and subsequent coupling of two or more CO moieties at transition metal centre remains a challenge. Herein, we report the use of low-coordinate iron(II) complexes for the selective scission and homologation of CO affording unusual squaraines and iron carboxylates at ambient temperature and pressures. A modification of the ligand framework allows for the isolation and structural characterisation of a proposed metallacyclic Fe(II) carbene intermediate. These results indicate that, with the appropriate choice of supporting ligands, it is possible to cleave and homologate carbon monoxide bonds under mild conditions using an abundant and environmentally benign low-coordinate, first row transition metal.

Citation

Sharpe, H. R., Geer, A. M., Taylor, L. J., Gridley, B. M., Blundell, T. J., Blake, A. J., Davies, E. S., Lewis, W., McMaster, J., Robinson, D., & Kays, D. L. (2018). Selective reduction and homologation of carbon monoxide by organometallic iron complexes. Nature Communications, 9, Article 3757. https://doi.org/10.1038/s41467-018-06242-w

• Journal Article Type: Article
• Acceptance Date: Aug 15, 2018
• Online Publication Date: Sep 14, 2018
• Publication Date: 2018-12
• Deposit Date: Aug 17, 2018
• Publicly Available Date: Sep 17, 2018
• Journal: Nature Communications
• Electronic ISSN: 2041-1723
• Publisher: Nature Publishing Group
• Peer Reviewed: Peer Reviewed
• Volume: 9
• Article Number: 3757
• DOI: https://doi.org/10.1038/s41467-018-06242-w
• Keywords: General Biochemistry, Genetics and Molecular Biology; General Physics and Astronomy; General Chemistry
• Public URL: https://nottingham-repository.worktribe.com/output/1037819
• Publisher URL: https://www.nature.com/articles/s41467-018-06242-w
• Contract Date: Sep 17, 2018