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. | |||
-INDIGO- | |||
===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=== | |||
{{#moleculelink:|link=UDPGSTPOVCEDJN-UHFFFAOYSA-L|image=true}} | |||
<chemform smiles="C1C2N3C=CN(C)C3[Ni+2](N#CC)3C4N(C(N=23)=CC=1)C=CN4C.F[P-](F)(F)(F)(F)F.F[P-](F)(F)(F)(F)F" inchi="1S/C13H17N5.C2H3N.2F6P.Ni/c1-15-6-8-17(10-15)12-4-3-5-13(14-12)18-9-7-16(2)11-18;1-2-3;2*1-7(2,3,4,5)6;/h3-9H,10-11H2,1-2H3;1H3;;;/q;;2*-1;+2" inchikey="XLAXHWSGDXWDSW-UHFFFAOYSA-N" height="200px" width="300px" float="none"> | |||
-INDIGO-11282314472D | |||
0 0 0 0 0 0 0 0 0 0 0 V3000 | 0 0 0 0 0 0 0 0 0 0 0 V3000 | ||
M V30 BEGIN CTAB | M V30 BEGIN CTAB | ||
M V30 COUNTS | M V30 COUNTS 36 38 0 0 0 | ||
M V30 BEGIN ATOM | M V30 BEGIN ATOM | ||
M V30 1 C 6.95985 -3.47507 0.0 0 | M V30 1 C 6.95985 -3.47507 0.0 0 | ||
| Line 30: | Line 40: | ||
M V30 17 C 5.13549 -7.55911 0.0 0 | M V30 17 C 5.13549 -7.55911 0.0 0 | ||
M V30 18 C 10.5145 -7.58411 0.0 0 | M V30 18 C 10.5145 -7.58411 0.0 0 | ||
M V30 19 Ni 7.85 -6.225 0.0 0 | M V30 19 Ni 7.85 -6.225 0.0 0 CHG=2 | ||
M V30 20 N 7.85 -7. | M V30 20 N 7.85 -7.75 0.0 0 | ||
M V30 21 C 7.85 -8. | M V30 21 C 7.85 -8.75 0.0 0 | ||
M V30 22 C 7.85 -9.225 0.0 0 | M V30 22 C 7.85 -9.75 0.0 0 | ||
M V30 23 F 12.092 -4.675 0.0 0 | |||
M V30 24 P 12.958 -4.175 0.0 0 CHG=-1 | |||
M V30 25 F 13.824 -4.675 0.0 0 | |||
M V30 26 F 12.958 -3.175 0.0 0 | |||
M V30 27 F 12.092 -3.675 0.0 0 | |||
M V30 28 F 13.824 -3.675 0.0 0 | |||
M V30 29 F 12.958 -5.175 0.0 0 | |||
M V30 30 F 12.359 -8.075 0.0 0 | |||
M V30 31 P 13.225 -7.575 0.0 0 CHG=-1 | |||
M V30 32 F 14.091 -8.075 0.0 0 | |||
M V30 33 F 13.225 -6.575 0.0 0 | |||
M V30 34 F 12.359 -7.075 0.0 0 | |||
M V30 35 F 14.091 -7.075 0.0 0 | |||
M V30 36 F 13.225 -8.575 0.0 0 | |||
M V30 END ATOM | M V30 END ATOM | ||
M V30 BEGIN BOND | M V30 BEGIN BOND | ||
| Line 62: | Line 86: | ||
M V30 25 3 20 21 | M V30 25 3 20 21 | ||
M V30 26 1 21 22 | M V30 26 1 21 22 | ||
M V30 27 1 23 24 | |||
M V30 28 1 24 25 | |||
M V30 29 1 24 26 | |||
M V30 30 1 24 27 | |||
M V30 31 1 24 28 | |||
M V30 32 1 24 29 | |||
M V30 33 1 30 31 | |||
M V30 34 1 31 32 | |||
M V30 35 1 31 33 | |||
M V30 36 1 31 34 | |||
M V30 37 1 31 35 | |||
M V30 38 1 31 36 | |||
M V30 END BOND | M V30 END BOND | ||
M V30 END CTAB | M V30 END CTAB | ||
| Line 67: | Line 103: | ||
</chemform> | </chemform> | ||
==== | ==Photosensitizer == | ||
{{#moleculelink: |link=NSABRUJKERBGOU-UHFFFAOYSA-N|image=true}} | |||
[[Category:Photocatalytic CO2 conversion to CO]] | |||
===Investigation === | |||
{{#experimentlist: |form=Photocatalytic_CO2_conversion_experiments|name=Photocatalytic CO2 reduction under varied conditions}} | |||
====Sacrificial Electron Donor==== | |||
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}}). | |||
====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. | |||
[[Category:Photocatalytic CO2 conversion to CO]][[Category:Publication]] | |||
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 |
Investigation-Name: Photocatalytic CO2 reduction under varied conditions
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)
