Nickel(II) pincer complexes demonstrate that the remote substituent controls catalytic carbon dioxide reduction: Difference between revisions
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===Abstract=== | ===Abstract=== | ||
====Summary==== | ====Summary==== | ||
A photochemical reduction of CO<sub>2</sub> to CO was shown using the nickel | A photochemical reduction of CO<sub>2</sub> to CO was shown using the nickel complex {{#moleculelink:|link=UDPGSTPOVCEDJN-UHFFFAOYSA-L|image=false|width=300|height=200}} in comparison to the inactive derivative {{#moleculelink:|link=XLAXHWSGDXWDSW-UHFFFAOYSA-N|image=false|width=300|height=200}} as catalyst in combination with the iridium-based photosensitizer {{#moleculelink:|link=NSABRUJKERBGOU-UHFFFAOYSA-N|image=false|width=300|height=200}}. Turnover numbers (TONs) of 10.6 for CO with the cobalt complex {{#moleculelink:|link=UDPGSTPOVCEDJN-UHFFFAOYSA-L|image=false|width=300|height=200}} were reached in acetonitrile. The experiments were conducted under visible-light irradiation using BIH and TEA as sacrificial electron donors (see section SEDs below). | ||
====Advances and special progress==== | ====Advances and special progress==== | ||
The authors showed the importance of remote substituents by a drastic change in activity through a change in a remote substituent. | The authors showed the importance of remote substituents by a drastic change in activity through a change in a remote substituent. | ||
Revision as of 15:29, 22 January 2024
Abstract
Summary
A photochemical reduction of CO2 to CO was shown using the nickel complex Ni(4O(-)py)-(MeNHC)2Cl in comparison to the inactive derivative [Ni(py)-(MeNHC)2(MeCN)][PF6]2 as catalyst in combination with the iridium-based photosensitizer Ir(ppy)3. Turnover numbers (TONs) of 10.6 for CO with the cobalt complex Ni(4O(-)py)-(MeNHC)2Cl were reached in acetonitrile. The experiments were conducted under visible-light irradiation using BIH and TEA as sacrificial electron donors (see section SEDs below).
Advances and special progress
The authors showed the importance of remote substituents by a drastic change in activity through a change in a remote substituent.
Additional remarks
The designed photocatalyst could be turned on and off via (de)protonation.
Content of the published article in detail
The article contains results for the reduction of CO2 to CO under visible-light catalysis using nickel complexes as catalysts. The catalytic system performs best (referring to the TON of CO production) in acetonitrile with the cobalt catalyst Ni(4O(-)py)-(MeNHC)2Cl.
Catalyst
Ni(4O(-)py)-(MeNHC)2Cl
[Ni(py)-(MeNHC)2(MeCN)][PF6]2
Photosensitizer
Investigation
Sacrificial Electron Donor
In this study, the experiments were done with the sacrificial electron donors BIH (BIH) and TEA (TEA).
Additives
In this study, TfOH and proton sponge were used as additives to (de)protonate the catalytically active nickel complex. Moreover, a control experiment under nitrogen atmosphere was conducted.
Investigations
- Photocatalytic CO2 reduction under varied conditions (Molecular process, Photocatalytic CO2 conversion experiments)
