Pyranopterin Related Dithiolene Molybdenum Complexes as Homogeneous Catalysts for CO2 Photoreduction: Difference between revisions

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{{#doiinfobox: 10.1002/anie.201809084}}
{{BaseTemplate}}
[[Category:Photocatalytic CO2 conversion to HCOOH]]
{{DOI|doi=10.1002/anie.201809084}}
===Abstract===
====Summary====
A photochemical reduction of CO<sub>2</sub> to formic acid or CO was shown using the novel dithiolene molybdenum complexes {{#moleculelink:|link=ZANCFLAGIYSVGM-UHFFFAOYSA-J|image=false|width=300|height=200}} and {{#moleculelink:|link=NXVSQECHHKIDOQ-UHFFFAOYSA-J|image=false|width=300|height=200}} in comparison to the previously reported complex {{#moleculelink:|link=SZEIOHNZAHLTPQ-UHFFFAOYSA-J|image=false|width=300|height=200}} as catalysts in combination with photosensitizer {{#moleculelink:|link=SJFYGUKHUNLZTK-UHFFFAOYSA-L|image=false|width=300|height=200}}. Turnover numbers (TONs) of  up to 83 for formic acid and 40 for CO were reached in acetonitrile for complex {{#moleculelink:|link=NXVSQECHHKIDOQ-UHFFFAOYSA-J|image=false|width=300|height=200}}. The experiments were conducted under visible-light irradiation (λ = 400 nm) using BIH and TEOA as sacrificial electron donor (see section SEDs below).
====Advances and special progress====
Bioinspired dithiolene Mo-complexes as analogues of the active site of the FDH (formate dehydrogenase) were shown to be active as CO<sub>2</sub> photoreduction catalysts with formation of formic acid as the main product.
 
====Additional remarks====
The developed complex {{#moleculelink:|link=NXVSQECHHKIDOQ-UHFFFAOYSA-J|image=false|width=300|height=200}} shows a similar TON for formic acid production to the previously synthesized complex {{#moleculelink:|link=SZEIOHNZAHLTPQ-UHFFFAOYSA-J|image=false|width=300|height=200}}, however a strong increase in selectivity is observed. The previously reported complex mainly catalyzes the generation of hydrogen.
 
===Content of the published article in detail===
The article contains results for the reduction of CO<sub>2</sub> to CO or formic acid under visible-light catalysis using molybdenum complexes and a ruthenium-based photosensitizer. The catalytic system performs best (referring to the TON of formic acid production) in acetonitrile with complex {{#moleculelink:|link=NXVSQECHHKIDOQ-UHFFFAOYSA-J|image=false|width=300|height=200}}.
==== Catalyst====
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  -INDIGO-01102415272D
 
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M  V30 66 1 58 61
M  V30 67 1 58 62
M  V30 68 1 59 63
M  V30 69 1 63 64
M  V30 70 1 64 65
M  V30 71 1 61 66
M  V30 72 1 66 67
M  V30 73 1 67 68
M  V30 74 1 62 69
M  V30 75 1 69 70
M  V30 76 1 70 71
M  V30 77 1 60 72
M  V30 78 1 72 73
M  V30 79 1 73 74
M  V30 END BOND
M  V30 END CTAB
M  END
</chemform>
 
====Photosensitizer====
<chemform smiles="" inchi="" inchikey="SJFYGUKHUNLZTK-UHFFFAOYSA-L" height="200px" width="300px" float="none"></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 ({{#moleculelink:|link=GSEJCLTVZPLZKY-UHFFFAOYSA-N|image=false|width=300|height=200}}) and BIH ({{#moleculelink:|link=VDFIVJSRRJXMAU-UHFFFAOYSA-N|image=false|width=300|height=200}}).
====Additives====
In this study, no additives were tested.
[[Category:Photocatalytic CO2 conversion to HCOOH]][[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 formic acid or CO was shown using the novel dithiolene molybdenum complexes [K]2[MoO(Hqpdt)2] and [MoO(2Hqpdt)2][NBu4] in comparison to the previously reported complex [MoO(qpdt)2][NBu4]2 as catalysts in combination with photosensitizer Ru(bpy)3Cl2. Turnover numbers (TONs) of up to 83 for formic acid and 40 for CO were reached in acetonitrile for complex [MoO(2Hqpdt)2][NBu4]. The experiments were conducted under visible-light irradiation (λ = 400 nm) using BIH and TEOA as sacrificial electron donor (see section SEDs below).

Advances and special progress[edit | edit source]

Bioinspired dithiolene Mo-complexes as analogues of the active site of the FDH (formate dehydrogenase) were shown to be active as CO2 photoreduction catalysts with formation of formic acid as the main product.

Additional remarks[edit | edit source]

The developed complex [MoO(2Hqpdt)2][NBu4] shows a similar TON for formic acid production to the previously synthesized complex [MoO(qpdt)2][NBu4]2, however a strong increase in selectivity is observed. The previously reported complex mainly catalyzes the generation of hydrogen.

Content of the published article in detail[edit | edit source]

The article contains results for the reduction of CO2 to CO or formic acid under visible-light catalysis using molybdenum complexes and a ruthenium-based photosensitizer. The catalytic system performs best (referring to the TON of formic acid production) in acetonitrile with complex [MoO(2Hqpdt)2][NBu4].

Catalyst[edit | edit source]

[K]2[MoO(Hqpdt)2] [MoO(2Hqpdt)2][NBu4] [MoO(qpdt)2][NBu4]2

Photosensitizer[edit | edit source]

Ru(bpy)3Cl2

Investigation[edit | edit source]

catcat conc [µM]PSPS conc [mM]e-De-D conc [M]solvent A...λexc [nm].TON COTON H2TON HCOOH.
1.

[MoO(qpdt)2][NBu4]2

0.05

Ru(bpy)3Cl2

0.5

BIH

0.1

MeCN

4007367080
2.

[K]2[MoO(Hqpdt)2]

0.05

Ru(bpy)3Cl2

0.5

BIH

0.1

MeCN

400135131
3.

[MoO(2Hqpdt)2][NBu4]

0.05

Ru(bpy)3Cl2

0.5

BIH

0.1

MeCN

400408983
Investigation-Name: Table 1

Sacrificial Electron Donor[edit | edit source]

In this study, the experiments were done with the sacrificial electron donors TEOA (TEOA) and BIH (BIH).

Additives[edit | edit source]

In this study, no additives were tested.

Investigations

  • Table 1 (Molecular process, Photocatalytic CO2 conversion experiments)
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