Pyranopterin Related Dithiolene Molybdenum Complexes as Homogeneous Catalysts for CO2 Photoreduction: Difference between revisions
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{{#doiinfobox: 10.1002/anie.201809084}} | {{#doiinfobox: 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==== | |||
====Additional remarks==== | |||
===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==== | ==== Catalyst==== | ||
<chemform smiles="[Mo-2](=O)1(~SC2C3=NC4C=CC=CC=4N(C)C3OC(C)(C)C=2S~1)1~SC2C(C)(C)OC3N(C)C4C=CC=CC=4N=C3C=2S~1.[K+].[K+]" inchi="1S/2C14H16N2OS2.2K.Mo.O/c2*1-14(2)12(19)11(18)10-13(17-14)16(3)9-7-5-4-6-8(9)15-10;;;;/h2*4-7,13,18-19H,1-3H3;;;;/q;;2*+1;+2;/p-4" inchikey="ZANCFLAGIYSVGM-UHFFFAOYSA-J" height="200px" width="300px" float="none"> | <chemform smiles="[Mo-2](=O)1(~SC2C3=NC4C=CC=CC=4N(C)C3OC(C)(C)C=2S~1)1~SC2C(C)(C)OC3N(C)C4C=CC=CC=4N=C3C=2S~1.[K+].[K+]" inchi="1S/2C14H16N2OS2.2K.Mo.O/c2*1-14(2)12(19)11(18)10-13(17-14)16(3)9-7-5-4-6-8(9)15-10;;;;/h2*4-7,13,18-19H,1-3H3;;;;/q;;2*+1;+2;/p-4" inchikey="ZANCFLAGIYSVGM-UHFFFAOYSA-J" height="200px" width="300px" float="none"> | ||
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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}}). | 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==== | ====Additives==== | ||
In this study, | In this study, no additives were tested. | ||
[[Category:Photocatalytic CO2 conversion to HCOOH]] | [[Category:Photocatalytic CO2 conversion to HCOOH]] | ||
Revision as of 11:05, 23 January 2024
Abstract
Summary
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
Additional remarks
Content of the published article in detail
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
[K]2[MoO(Hqpdt)2]
[MoO(2Hqpdt)2][NBu4]
[MoO(qpdt)2][NBu4]2
Photosensitizer
Investigation
| cat | cat conc [µM] | PS | PS conc [mM] | e-D | e-D conc [M] | solvent A | . | . | . | λexc [nm] | . | TON CO | TON H2 | TON HCOOH | . | |
|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|
| 1. | 0.05 | 0.5 | 0.1 | 400 | 73 | 670 | 80 | |||||||||
| 2. | 0.05 | 0.5 | 0.1 | 400 | 13 | 51 | 31 | |||||||||
| 3. | 0.05 | 0.5 | 0.1 | 400 | 40 | 89 | 83 |
Sacrificial Electron Donor
In this study, the experiments were done with the sacrificial electron donors TEOA (TEOA) and BIH (BIH).
Additives
In this study, no additives were tested.
Investigations
- Table 1 (Molecular process, Photocatalytic CO2 conversion experiments)
