Editing Visible-Light Photocatalytic Conversion of Carbon Dioxide by Ni(II) Complexes with N4S2 Coordination: Highly Efficient and Selective Production of Formate

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{{DOI|doi=10.1021/jacs.0c08145}}
===Abstract===
====Summary====
A photochemical reduction of CO<sub>2</sub> to formate was shown using the nickel complexes {{#moleculelink:|link=CLQAFMRCKIGWOF-UHFFFAOYSA-L|image=false|width=300|height=200}} or {{#moleculelink:|link=BDPUYSVREMMVBP-UHFFFAOYSA-L|image=false|width=300|height=200}} as catalysts in combination with the organic photosensitizer {{#moleculelink:|link=SEACYXSIPDVVMV-UHFFFAOYSA-L|image=false|width=300|height=200}}. Turnover numbers (TONs) of  up to 14000 and a selectivity of >99% for formate were reached in ethanol/water. The experiments were conducted under visible-light irradiation (λ > 400 nm) using TEOA as sacrificial electron donor (see section SEDs below).
====Advances and special progress====
A set of bioinspired nickel complexes have been developed and shown to possess remarkably high efficiencies and selectivities as catalysts in CO<sub>2</sub> reduction, being the (at that time) best early transition metal complexes for photocatalytic CO<sub>2</sub> conversion.

====Additional remarks====
The nickel complexes were also active catalysts for hydrogen photoreduction under argon atmosphere.

===Content of the published article in detail===
The article contains results for the reduction of CO<sub>2</sub> to formate under visible-light catalysis using nickel complexes and an organic photosensitizer. The catalytic system performs best (referring to the TON of formate production) in ethanol/water with complex {{#moleculelink:|link=CLQAFMRCKIGWOF-UHFFFAOYSA-L|image=false|width=300|height=200}} as a catalyst.

==== Catalyst ====
<chemform smiles="C1C=CC=N2[Ni+2]3([S-]C4N3=CC=CC=4)3([S-]C4=CC=CC=N43)N3=C(NC4C=CC=CC=43)C=12" inchikey="CLQAFMRCKIGWOF-UHFFFAOYSA-L" inchi="1S/C12H9N3.2C5H5NS.Ni/c1-2-6-10-9(5-1)14-12(15-10)11-7-3-4-8-13-11;2*7-5-3-1-2-4-6-5;/h1-8H,(H,14,15);2*1-4H,(H,6,7);/q;;;+2/p-2" float="none" width="300" height="200">
  -INDIGO-11302312462D

  0  0  0  0  0  0  0  0  0  0  0 V3000
M  V30 BEGIN CTAB
M  V30 COUNTS 30 37 0 0 0
M  V30 BEGIN ATOM
M  V30 1 C 4.22629 -7.80601 0.0 0
M  V30 2 N 5.90948 -7.56855 0.0 0
M  V30 3 C 4.96703 -7.24549 0.0 0
M  V30 4 C 6.08213 -8.50205 0.0 0
M  V30 5 C 4.36141 -8.74382 0.0 0
M  V30 6 C 5.29809 -9.11534 0.0 0
M  V30 7 C 4.92207 -6.38756 0.0 0
M  V30 8 N 4.11814 -5.81174 0.0 0
M  V30 9 C 4.47217 -4.9117 0.0 0
M  V30 10 C 5.45493 -4.93524 0.0 0
M  V30 11 N 5.71267 -5.91607 0.0 0
M  V30 12 C 3.95563 -4.10265 0.0 0
M  V30 13 C 4.43773 -3.2562 0.0 0
M  V30 14 C 5.97573 -4.1409 0.0 0
M  V30 15 C 5.46132 -3.25564 0.0 0
M  V30 16 C 8.19043 -5.02095 0.0 0
M  V30 17 C 9.64906 -4.15013 0.0 0
M  V30 18 C 8.6395 -4.13871 0.0 0
M  V30 19 C 10.0934 -5.02704 0.0 0
M  V30 20 N 8.55109 -5.74026 0.0 0
M  V30 21 C 9.5156 -5.85055 0.0 0
M  V30 22 N 8.5589 -7.14296 0.0 0
M  V30 23 C 10.2084 -7.55589 0.0 0
M  V30 24 C 9.5038 -6.86005 0.0 0
M  V30 25 C 9.92498 -8.50582 0.0 0
M  V30 26 C 8.33576 -7.91156 0.0 0
M  V30 27 C 8.93402 -8.69908 0.0 0
M  V30 28 S 7.12277 -8.08302 0.0 0 CHG=-1
M  V30 29 Ni 7.04952 -6.51544 0.0 0 CHG=2
M  V30 30 S 6.97788 -5.00244 0.0 0 CHG=-1
M  V30 END ATOM
M  V30 BEGIN BOND
M  V30 1 2 3 1
M  V30 2 2 4 2
M  V30 3 1 1 5
M  V30 4 1 2 3
M  V30 5 2 5 6
M  V30 6 1 6 4
M  V30 7 1 3 7
M  V30 8 1 7 8
M  V30 9 1 8 9
M  V30 10 2 9 10
M  V30 11 1 10 11
M  V30 12 2 11 7
M  V30 13 2 13 12
M  V30 14 1 10 14
M  V30 15 1 12 9
M  V30 16 2 14 15
M  V30 17 1 15 13
M  V30 18 2 18 16
M  V30 19 2 19 17
M  V30 20 1 16 20
M  V30 21 1 17 18
M  V30 22 2 20 21
M  V30 23 1 21 19
M  V30 24 2 24 22
M  V30 25 2 25 23
M  V30 26 1 22 26
M  V30 27 1 23 24
M  V30 28 2 26 27
M  V30 29 1 27 25
M  V30 30 1 26 28
M  V30 31 10 20 29
M  V30 32 10 11 29
M  V30 33 10 2 29
M  V30 34 10 22 29
M  V30 35 10 28 29
M  V30 36 1 16 30
M  V30 37 10 30 29
M  V30 END BOND
M  V30 END CTAB
M  END
</chemform><chemform smiles="C1C=CC=N2[Ni](N3=C(SC4C=CC=CC=43)C=12)1(N2C(S~1)=CC=CC=2)1N2C=CC=CC=2S~1" inchi="1S/C12H8N2S.2C5H5NS.Ni/c1-2-7-11-9(5-1)14-12(15-11)10-6-3-4-8-13-10;2*7-5-3-1-2-4-6-5;/h1-8H;2*1-4H,(H,6,7);/q;;;+2/p-2" inchikey="BDPUYSVREMMVBP-UHFFFAOYSA-L" height="200px" width="300px" float="none">
  -INDIGO-01252311232D

  0  0  0  0  0  0  0  0  0  0  0 V3000
M  V30 BEGIN CTAB
M  V30 COUNTS 30 37 0 0 0
M  V30 BEGIN ATOM
M  V30 1 C 4.11328 -6.99588 0.0 0
M  V30 2 N 5.97043 -6.96694 0.0 0
M  V30 3 C 5.06556 -6.51543 0.0 0
M  V30 4 C 5.83962 -7.95822 0.0 0
M  V30 5 C 4.04457 -7.85785 0.0 0
M  V30 6 C 4.80838 -8.37469 0.0 0
M  V30 7 N 8.53748 -6.34335 0.0 0
M  V30 8 C 10.0947 -6.56358 0.0 0
M  V30 9 C 9.28611 -6.01049 0.0 0
M  V30 10 C 10.0878 -7.47584 0.0 0
M  V30 11 C 8.46263 -7.17926 0.0 0
M  V30 12 C 9.29975 -7.86191 0.0 0
M  V30 13 C 9.72395 -4.21259 0.0 0
M  V30 14 N 8.38205 -4.95994 0.0 0
M  V30 15 C 9.17536 -4.97982 0.0 0
M  V30 16 C 8.08655 -4.2472 0.0 0
M  V30 17 C 9.46404 -3.43675 0.0 0
M  V30 18 C 8.6765 -3.34062 0.0 0
M  V30 19 C 5.01674 -5.7858 0.0 0
M  V30 20 S 4.32965 -5.22897 0.0 0
M  V30 21 C 4.62248 -4.40093 0.0 0
M  V30 22 C 5.63863 -4.4363 0.0 0
M  V30 23 N 5.96848 -5.24313 0.0 0
M  V30 24 C 4.18681 -3.69801 0.0 0
M  V30 25 C 4.65187 -2.96412 0.0 0
M  V30 26 C 5.99621 -3.7537 0.0 0
M  V30 27 C 5.57138 -2.99334 0.0 0
M  V30 28 S 7.16543 -4.54732 0.0 0
M  V30 29 S 7.45355 -7.19354 0.0 0
M  V30 30 Ni 7.28742 -5.90094 0.0 0
M  V30 END ATOM
M  V30 BEGIN BOND
M  V30 1 2 3 1
M  V30 2 2 4 2
M  V30 3 1 1 5
M  V30 4 1 2 3
M  V30 5 2 5 6
M  V30 6 1 6 4
M  V30 7 2 9 7
M  V30 8 2 10 8
M  V30 9 1 7 11
M  V30 10 1 8 9
M  V30 11 2 11 12
M  V30 12 1 12 10
M  V30 13 2 15 13
M  V30 14 2 16 14
M  V30 15 1 13 17
M  V30 16 1 14 15
M  V30 17 2 17 18
M  V30 18 1 18 16
M  V30 19 1 3 19
M  V30 20 1 19 20
M  V30 21 1 20 21
M  V30 22 2 21 22
M  V30 23 1 22 23
M  V30 24 2 23 19
M  V30 25 2 25 24
M  V30 26 1 22 26
M  V30 27 1 24 21
M  V30 28 2 26 27
M  V30 29 1 27 25
M  V30 30 1 16 28
M  V30 31 1 11 29
M  V30 32 8 29 30
M  V30 33 8 28 30
M  V30 34 10 14 30
M  V30 35 10 7 30
M  V30 36 10 2 30
M  V30 37 10 23 30
M  V30 END BOND
M  V30 END CTAB
M  END
</chemform>

====Photosensitizer====
{{#moleculelink:|link=SEACYXSIPDVVMV-UHFFFAOYSA-L|image=true|width=300|height=200}}

====Investigation====
{{#experimentlist:|form=Photocatalytic_CO2_conversion_experiments|name=Table 1}}

==== Sacrificial Electron Donor ====
In this study, the experiments were done with the sacrificial electron donor TEOA ([[Molecule:100507|triethanolamine]]).

==== Additives ====
In this study, no additives were tested. 
[[Category:Photocatalytic CO2 conversion to HCOOH]]