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

2018 | journal article; research paper. A publication with affiliation to the University of Göttingen.

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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.   & Schneider, S. ​ (2018) 
Nature Communications9(1) art. 1161​.​ DOI: https://doi.org/10.1038/s41467-018-03239-3 

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Authors
Schneck, Felix ; Ahrens, Jennifer; Finger, Markus ; Stückl, Andrea Claudia ; Würtele, Christian ; Schwarzer, Dirk ; Schneider, Sven 
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.
Issue Date
2018
Journal
Nature Communications 
Project
info:eu-repo/grantAgreement/EC/H2020/646747/EU//N2FEED
SFB 1073: Kontrolle von Energiewandlung auf atomaren Skalen 
SFB 1073 | Topical Area C | C07 Kontrolle Reaktivität hydridischer Photokatalysatoren 
Organization
Institut für Anorganische Chemie ; Max-Planck-Institut für Biophysikalische Chemie 
ISSN
2041-1723
Language
English

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