Nickel(II) pincer complexes demonstrate that the remote substituent controls catalytic carbon dioxide reduction: Difference between revisions
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{{ | {{DOI|doi=10.1039/c7cc09507d}} | ||
===Abstract=== | |||
====Summary==== | |||
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==== | |||
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 CO<sub>2</sub> 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 {{#moleculelink:|link=UDPGSTPOVCEDJN-UHFFFAOYSA-L|image=false|width=300|height=200}}. | |||
===Catalyst=== | ===Catalyst=== | ||
{{#moleculelink:|link=UDPGSTPOVCEDJN-UHFFFAOYSA-L|image=true}} | {{#moleculelink:|link=UDPGSTPOVCEDJN-UHFFFAOYSA-L|image=true}} | ||
| Line 92: | Line 103: | ||
</chemform> | </chemform> | ||
==Photosensitizer == | |||
{{#moleculelink:|link= | {{#moleculelink: |link=NSABRUJKERBGOU-UHFFFAOYSA-N|image=true}} | ||
===Investigation === | ===Investigation === | ||
{{#experimentlist:|form=Photocatalytic_CO2_conversion_experiments|name= | {{#experimentlist: |form=Photocatalytic_CO2_conversion_experiments|name=Photocatalytic CO2 reduction under varied conditions}} | ||
====Sacrificial Electron Donor==== | |||
===Sacrificial | In this study, the experiments were done with the sacrificial electron donors BIH ({{#moleculelink:|link=VDFIVJSRRJXMAU-UHFFFAOYSA-N|image=false|width=300|height=200}}) and TEA ({{#moleculelink: |link=ZMANZCXQSJIPKH-UHFFFAOYSA-N|image=false|width=300|height=200}}). | ||
{{#moleculelink:|link=VDFIVJSRRJXMAU-UHFFFAOYSA-N|image= | ====Additives==== | ||
In this study, {{#moleculelink:|link=ITMCEJHCFYSIIV-UHFFFAOYSA-N|image=false|width=300|height=200}} and proton sponge were used as additives to (de)protonate the catalytically active nickel complex. Moreover, a control experiment under nitrogen atmosphere was conducted. | |||
===Additives=== | [[Category:Photocatalytic CO2 conversion to CO]][[Category:Publication]] | ||
[[Category:Photocatalytic CO2 conversion to CO]] | |||
Latest revision as of 10:37, 11 April 2024
Abstract[edit | edit source]
Summary[edit | edit source]
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[edit | edit source]
The authors showed the importance of remote substituents by a drastic change in activity through a change in a remote substituent.
Additional remarks[edit | edit source]
The designed photocatalyst could be turned on and off via (de)protonation.
Content of the published article in detail[edit | edit source]
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[edit | edit source]
Ni(4O(-)py)-(MeNHC)2Cl
[Ni(py)-(MeNHC)2(MeCN)][PF6]2
Photosensitizer[edit | edit source]
Investigation[edit | edit source]
| cat | cat conc [µM] | PS | PS conc [mM] | e-D | e-D conc [M] | solvent A | additives | λexc [nm] | TON CO | . | |
|---|---|---|---|---|---|---|---|---|---|---|---|
| 1. | 0.1 | 0.1 | 0.011 | TEA | solar spectrum | 10.6 | |||||
| 2. | 0.1 | 0.1 | 0.011 | TEA | solar spectrum | 0.1 | |||||
| 3. | 0.1 | 0.1 | 0.011 | TEA | solar spectrum | 9 | |||||
| 4. | 0.1 | 0.1 | 0.011 | TEA | solar spectrum | 0.5 | |||||
| 5. | 0.1 | 0.1 | 0.011 | solar spectrum | 1.8 | ||||||
| 6. | 0.1 | 0.1 | 0.011 | proton sponge | solar spectrum | 5.6 | |||||
| 7. | 0.1 | 0.1 | 0.011 | TfOH | solar spectrum | 0.9 | |||||
| 8. | 0.1 | 0.011 | TEA | solar spectrum | 0.6 | ||||||
| 9. | 0.1 | 0.1 | TEA | solar spectrum | 0.3 | ||||||
| 10. | 0.1 | 0.1 | 0.011 | N2 | solar spectrum | 0.2 |
Sacrificial Electron Donor[edit | edit source]
In this study, the experiments were done with the sacrificial electron donors BIH (BIH) and TEA (TEA).
Additives[edit | edit source]
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)
