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  The elusive abnormal CO2 insertion enabled by metal-ligand cooperative photochemical selectivity inversion.

Schneck, F., Ahrens, J., Finger, M., Stückl, A. C., Würtele, C., Schwarzer, D., et al. (2018). The elusive abnormal CO2 insertion enabled by metal-ligand cooperative photochemical selectivity inversion. Nature Communications, 9: 1161. doi:10.1038/s41467-018-03239-3.

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Item Permalink: http://hdl.handle.net/21.11116/0000-0000-F980-6 Version Permalink: http://hdl.handle.net/21.11116/0000-0003-B427-6
Genre: Journal Article

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Schneck, F., Author
Ahrens, J.1, Author              
Finger, M., Author
Stückl, A. C., Author
Würtele, C., Author
Schwarzer, D.1, Author              
Schneider, S., Author
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1Department of Dynamics at Surfaces, MPI for Biophysical Chemistry, Max Planck Society, ou_578600              

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 Abstract: Direct hydrogenation of CO2 to CO, the reverse water-gas shift reaction, is an attractive route to CO2 utilization. However, the use of molecular catalysts is impeded by the general reactivity of metal hydrides with CO2. Insertion into M-H bonds results in formates (MO(O)CH), whereas the abnormal insertion to the hydroxycarbonyl isomer (MC(O)OH), which is the key intermediate for CO-selective catalysis, has never been directly observed. We here report that the selectivity of CO2 insertion into a Ni-H bond can be inverted from normal to abnormal insertion upon switching from thermal to photochemical conditions. Mechanistic examination for abnormal insertion indicates photochemical N-H reductive elimination as the pivotal step that leads to an umpolung of the hydride ligand. This study conceptually introduces metal-ligand cooperation for selectivity control in photochemical transformations.

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Language(s): eng - English
 Dates: 2018-03-21
 Publication Status: Published online
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 Rev. Method: Peer
 Identifiers: DOI: 10.1038/s41467-018-03239-3
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Title: Nature Communications
Source Genre: Journal
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Pages: 8 Volume / Issue: 9 Sequence Number: 1161 Start / End Page: - Identifier: -