Editing Visible-Light-Driven Photocatalytic CO2 Reduction by a Ni(II) Complex Bearing a Bioinspired Tetradentate Ligand for Selective CO Production

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{{DOI|doi=10.1021/jacs.7b01956}}

=== Abstract ===

==== Summary ====
A photochemical reduction of CO<sub>2</sub> to CO was shown using the nickel complex {{#moleculelink:|link=SOBXSEUOEROXNJ-UHFFFAOYSA-L|image=false|width=300|height=200}} as catalyst in combination with the ruthenium-based photosensitizer {{#moleculelink:|link=SJFYGUKHUNLZTK-UHFFFAOYSA-L|image=false|width=300|height=200}}. Turnover numbers (TONs) over 700 and a selectivity of >99% for CO were reached in dimethylacetamide/water. The experiments were conducted under visible-light irradiation (λ = 450 nm) using BIH as sacrificial reductants (see section SEDs below).

==== Advances and special progress ====
A nickel catalyst inspired by the CODH enzyme (carbon monoxide dehydrogenase) was employed for the photocatalytic reduction of CO<sub>2</sub> with the back then highest reported TON values among nickel complexes in systems with [Ru(bpy)<sub>3</sub>]<sup>2+</sup>.

==== Additional remarks ====
The binding of CO<sub>2</sub> to the nickel(0) species was identified as the potential rate-determining step of the reduction.

=== 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 a nickel complex as a catalyst. The catalytic system performs best (referring to the TON of CO production) in dimethylacetamide/water.

==== Catalyst====
{{#moleculelink:|link=SOBXSEUOEROXNJ-UHFFFAOYSA-L|image=true}}

====Photosensitizer====
<chemform smiles="C1C=N2[Ru+2]3(N4C(C5N3=CC=CC=5)=CC=CC=4)3(N4=CC=CC=C4C4=CC=CC=N43)N3=CC=CC=C3C2=CC=1.[Cl-].[Cl-]" inchi="1S/3C10H8N2.2ClH.Ru/c3*1-3-7-11-9(5-1)10-6-2-4-8-12-10;;;/h3*1-8H;2*1H;/q;;;;;+2/p-2" inchikey="SJFYGUKHUNLZTK-UHFFFAOYSA-L" height="200px" width="300px" float="none">
  -INDIGO-11272316582D

  0  0  0  0  0  0  0  0  0  0  0 V3000
M  V30 BEGIN CTAB
M  V30 COUNTS 39 45 0 0 0
M  V30 BEGIN ATOM
M  V30 1 C 8.38485 -1.67507 0.0 0
M  V30 2 C 10.1152 -1.67459 0.0 0
M  V30 3 C 9.25164 -1.17497 0.0 0
M  V30 4 C 10.1152 -2.67553 0.0 0
M  V30 5 C 8.38485 -2.68002 0.0 0
M  V30 6 N 9.25382 -3.17503 0.0 0
M  V30 7 C 10.9812 -3.17553 0.0 0
M  V30 8 C 12.7115 -3.17389 0.0 0
M  V30 9 C 11.8476 -2.67484 0.0 0
M  V30 10 C 12.7121 -4.17483 0.0 0
M  V30 11 N 10.9818 -4.18048 0.0 0
M  V30 12 C 11.8512 -4.67491 0.0 0
M  V30 13 N 10.9848 -6.20007 0.0 0
M  V30 14 C 12.7152 -6.19959 0.0 0
M  V30 15 C 11.8516 -5.69997 0.0 0
M  V30 16 C 12.7152 -7.20053 0.0 0
M  V30 17 C 10.9848 -7.20502 0.0 0
M  V30 18 C 11.8538 -7.70003 0.0 0
M  V30 19 C 10.1188 -7.70502 0.0 0
M  V30 20 C 9.2551 -9.20433 0.0 0
M  V30 21 C 10.1192 -8.70573 0.0 0
M  V30 22 C 8.38792 -8.70444 0.0 0
M  V30 23 N 9.24818 -7.20313 0.0 0
M  V30 24 C 8.38534 -7.70875 0.0 0
M  V30 25 C 5.70985 -6.27507 0.0 0
M  V30 26 N 7.44015 -6.27459 0.0 0
M  V30 27 C 6.57664 -5.77497 0.0 0
M  V30 28 C 7.44015 -7.27553 0.0 0
M  V30 29 C 5.70985 -7.28002 0.0 0
M  V30 30 C 6.57882 -7.77503 0.0 0
M  V30 31 C 6.57664 -4.77497 0.0 0
M  V30 32 C 5.71006 -3.2773 0.0 0
M  V30 33 C 5.7098 -4.27494 0.0 0
M  V30 34 C 6.57657 -2.77625 0.0 0
M  V30 35 N 7.44661 -4.27191 0.0 0
M  V30 36 C 7.44015 -3.27186 0.0 0
M  V30 37 Ru 9.21263 -5.19691 0.0 0 CHG=2
M  V30 38 Cl 14.05 -1.95 0.0 0 CHG=-1
M  V30 39 Cl 14.1 -3.225 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 4 7
M  V30 8 2 9 7
M  V30 9 2 10 8
M  V30 10 1 7 11
M  V30 11 1 8 9
M  V30 12 2 11 12
M  V30 13 1 12 10
M  V30 14 2 15 13
M  V30 15 2 16 14
M  V30 16 1 13 17
M  V30 17 1 14 15
M  V30 18 2 17 18
M  V30 19 1 18 16
M  V30 20 1 17 19
M  V30 21 2 21 19
M  V30 22 2 22 20
M  V30 23 1 19 23
M  V30 24 1 20 21
M  V30 25 2 23 24
M  V30 26 1 24 22
M  V30 27 2 27 25
M  V30 28 2 28 26
M  V30 29 1 25 29
M  V30 30 1 26 27
M  V30 31 2 29 30
M  V30 32 1 30 28
M  V30 33 1 27 31
M  V30 34 2 33 31
M  V30 35 2 34 32
M  V30 36 1 31 35
M  V30 37 1 32 33
M  V30 38 2 35 36
M  V30 39 1 36 34
M  V30 40 10 35 37
M  V30 41 10 6 37
M  V30 42 10 37 11
M  V30 43 10 13 37
M  V30 44 10 37 23
M  V30 45 10 26 37
M  V30 END BOND
M  V30 END CTAB
M  END
</chemform>

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

==== Sacrificial electron donor ====
In this study, the experiments were done with the sacrificial electron donors TEOA ([[Molecule:100507|100507]]), BIH ([[Molecule:100508|100508]]), and TEA ([[Molecule:100505|100505]]).

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