Nickel(II) pincer complexes demonstrate that the remote substituent controls catalytic carbon dioxide reduction: Difference between revisions

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DOI 10.1039/c7cc09507d
Authors Dalton B. Burks, Shakeyia Davis, Robert W. Lamb, Xuan Liu, Roberta R. Rodrigues, Nalaka P. Liyanage, Yujie Sun, Charles Edwin Webster, Jared H. Delcamp, Elizabeth T. Papish,
Submitted 13.03.2018
Published online 2018
Licenses http://rsc.li/journals-terms-of-use#chorus,
Subjects Materials Chemistry, Metals and Alloys, Surfaces, Coatings and Films, General Chemistry, Ceramics and Composites, Electronic, Optical and Magnetic Materials, Catalysis
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{{#doiinfobox: 10.1039/c7cc09507d}}
{{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=QFRHHPFUSKJYCI-UHFFFAOYSA-L|image=true}}
{{#moleculelink:|link=UDPGSTPOVCEDJN-UHFFFAOYSA-L|image=true}}
<chemform smiles="C1C2N3C=CN(C)C3[Ni](N#CC)3C4N(C(N=23)=CC=1)C=CN4C" inchi="1S/C13H17N5.C2H3N.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;/h3-9H,10-11H2,1-2H3;1H3;" inchikey="WWQONKLZHTWXPP-UHFFFAOYSA-N" height="200px" width="300px" float="none">
<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-01272314332D
   -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 22 26 0 0 0
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 29: 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 -7.225 0.0 0
M  V30 20 N 7.85 -7.75 0.0 0
M  V30 21 C 7.85 -8.225 0.0 0
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 61: 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 66: Line 103:
</chemform>
</chemform>


===Photosensitizer ===
==Photosensitizer ==
{{#moleculelink:|link=UEEXRMUCXBPYOV-UHFFFAOYSA-N|image=true}}
{{#moleculelink: |link=NSABRUJKERBGOU-UHFFFAOYSA-N|image=true}}


===Investigation ===
===Investigation ===
{{#experimentlist:|form=Photocatalytic_CO2_conversion_experiments|name=Table 1}}
{{#experimentlist: |form=Photocatalytic_CO2_conversion_experiments|name=Photocatalytic CO2 reduction under varied conditions}}
 
====Sacrificial Electron Donor====
===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}}).
{{#moleculelink:|link=VDFIVJSRRJXMAU-UHFFFAOYSA-N|image=true}}{{#moleculelink:|link=ZMANZCXQSJIPKH-UHFFFAOYSA-N|image=true}}
====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]]
<chemform smiles="C(F)(F)(F)S(=O)(=O)O" inchi="1S/CHF3O3S/c2-1(3,4)8(5,6)7/h(H,5,6,7)" inchikey="ITMCEJHCFYSIIV-UHFFFAOYSA-N" height="200px" width="300px" float="none">
  -INDIGO-05042311232D
 
  0  0  0  0  0  0  0  0  0  0  0 V3000
M  V30 BEGIN CTAB
M  V30 COUNTS 8 7 0 0 0
M  V30 BEGIN ATOM
M  V30 1 C 6.1 -3.95 0.0 0
M  V30 2 S 6.6 -4.81603 0.0 0
M  V30 3 F 5.1 -3.95 0.0 0
M  V30 4 F 5.6 -3.08397 0.0 0
M  V30 5 F 6.6 -3.08397 0.0 0
M  V30 6 O 5.89289 -5.52313 0.0 0
M  V30 7 O 7.30711 -4.10892 0.0 0
M  V30 8 O 7.56593 -5.07484 0.0 0
M  V30 END ATOM
M  V30 BEGIN BOND
M  V30 1 1 1 2
M  V30 2 1 1 3
M  V30 3 1 1 4
M  V30 4 1 1 5
M  V30 5 1 2 6
M  V30 6 2 2 7
M  V30 7 2 2 8
M  V30 END BOND
M  V30 END CTAB
M  END
</chemform>
[[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]

Ir(ppy)3

Investigation[edit | edit source]

catcat conc [µM]PSPS conc [mM]e-De-D conc [M]solvent Aadditivesλexc [nm]TON CO.
1.

Ni(4O(-)py)-(MeNHC)2Cl

0.1

Ir(ppy)3

0.1

BIH

0.011

MeCN

TEAsolar spectrum10.6
2.

[Ni(py)-(MeNHC)2(MeCN)][PF6]2

0.1

Ir(ppy)3

0.1

BIH

0.011

MeCN

TEAsolar spectrum0.1
3.

Ni(4O(-)py)-(MeNHC)2Cl

0.1

Ir(ppy)3

0.1

BIH

0.011

DMF

TEAsolar spectrum9
4.

[Ni(py)-(MeNHC)2(MeCN)][PF6]2

0.1

Ir(ppy)3

0.1

BIH

0.011

DMF

TEAsolar spectrum0.5
5.

Ni(4O(-)py)-(MeNHC)2Cl

0.1

Ir(ppy)3

0.1

BIH

0.011

MeCN

solar spectrum1.8
6.

Ni(4O(-)py)-(MeNHC)2Cl

0.1

Ir(ppy)3

0.1

BIH

0.011

MeCN

proton spongesolar spectrum5.6
7.

Ni(4O(-)py)-(MeNHC)2Cl

0.1

Ir(ppy)3

0.1

BIH

0.011

MeCN

TfOHsolar spectrum0.9
8.

Ni(4O(-)py)-(MeNHC)2Cl

0.1


BIH

0.011

MeCN

TEAsolar spectrum0.6
9.

Ni(4O(-)py)-(MeNHC)2Cl

0.1

Ir(ppy)3

0.1


MeCN

TEAsolar spectrum0.3
10.

Ni(4O(-)py)-(MeNHC)2Cl

0.1

Ir(ppy)3

0.1

BIH

0.011

MeCN

N2solar spectrum0.2

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

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