A Highly Durable, Self-Photosensitized Mononuclear Ruthenium Catalyst for CO2 Reduction

Kenji Kamada; Hiroko Okuwa; Taku Wakabayashi; Keita Sekizawa; Shunsuke Sato; Takeshi Morikawa; Jieun Jung; Susumu Saito

doi:10.1055/a-1709-0280

Synlett, Table of Contents

Synlett 2022; 33(12): 1137-1141
DOI: 10.1055/a-1709-0280

cluster

Organic Photoredox Catalysis in Synthesis – Honoring Prof. Shunichi Fukuzumi’s 70th Birthday

A Highly Durable, Self-Photosensitized Mononuclear Ruthenium Catalyst for CO₂ Reduction

Kenji Kamada

^aDepartment of Chemistry, Graduate School of Science, Nagoya University, Chikusa, Nagoya 464-8602, Japan

,

Hiroko Okuwa

^aDepartment of Chemistry, Graduate School of Science, Nagoya University, Chikusa, Nagoya 464-8602, Japan

,

Taku Wakabayashi

^aDepartment of Chemistry, Graduate School of Science, Nagoya University, Chikusa, Nagoya 464-8602, Japan

,

Keita Sekizawa

^bToyota Central R&D Laboratories, Inc., Nagakute 480-1192, Japan

,

Shunsuke Sato

^bToyota Central R&D Laboratories, Inc., Nagakute 480-1192, Japan

,

Takeshi Morikawa

^bToyota Central R&D Laboratories, Inc., Nagakute 480-1192, Japan

,

Jieun Jung∗

^aDepartment of Chemistry, Graduate School of Science, Nagoya University, Chikusa, Nagoya 464-8602, Japan

,

Susumu Saito ∗

^aDepartment of Chemistry, Graduate School of Science, Nagoya University, Chikusa, Nagoya 464-8602, Japan

^cResearch Center for Materials Science (RCMS), Nagoya University, Chikusa, Nagoya 464-8602, Japan

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Abstract

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Abstract

A novel mononuclear ruthenium (Ru) complex bearing a PNNP-type tetradentate ligand is introduced here as a self-photosensitized catalyst for the reduction of carbon dioxide (CO₂). When the pre-activation of the Ru complex by reaction with a base was carried out, an induction period of catalyst almost disappeared and the catalyst turnover numbers (TONs) over a reaction time of 144 h reached 307 and 489 for carbon monoxide (CO) and for formic acid (HCO₂H), respectively. The complex has a long lifespan as a dual photosensitizer and reduction catalyst, due to the sterically bulky and structurally robust (PNNP)Ru framework. Isotope-labeling experiments under ¹³CO₂ atmosphere indicate that CO and HCO₂H were both produced from CO₂.

Key words

CO₂ reduction - photocatalyst - ruthenium complex - carbon monoxide - formic acid

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References

References and Notes

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19 Experimental Conditions Photocatalytic reactions were performed at atmospheric pressure in 8 mL test tubes containing 4 mL of a DMA/TEOA (5:1 v/v) solution purged with CO₂ for 10 min, a Ru complex (0.1 mM), and BIH (0.10 M). The solutions were irradiated in a turntable irradiation apparatus at room temperature using a Xe lamp (300 W) combined with a UV-cut filter having a cutoff wavelength of below 400 nm and a UV- and IR-cut filter ranging from 385 nm to 740 nm. The gaseous reaction products were analyzed using a micro-GC (Agilent 490) equipped with a thermal conductivity detector (column: MS5A 10-m BF column; isothermal at 80 °C; carrier gas: Ar), and the products in the solution were analyzed using Prominence Organic Acid Analysis System (SCR-102H column; column temp: 40 °C; cell temp: 43 °C). The reaction set-up is shown in Figure S11 (see the Supporting Information).
20 Pre-activation of Ru-1 with a 2–8 equiv of KOt-Bu gave UV/Vis absorption spectra almost identical with one another, indicating that the photoactive complex is stable in the presence of excess KOt-Bu (Figure S3). Although ¹H NMR (CD₃CN) measurements of Ru-1·2KOt-Bu showed a RuH signal (J _P–H = 26.4 Hz, triplet) at –16.3 ppm, it was difficult to determine the exact structure due to the overall intractable/inscrutable spectrum (Figures S19). In Figure S2, the structure of the pre-activated Ru complex was proposed merely on the basis of ESI-(HR)MS measurement.
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23 DFT calculations of the HOMO–LUMO gaps of Ru-1 and the proposed structure of the pre-activated Ru complex which lost Cl^– and a bipyridyl CH₂P hydrogen also suggest that the complex which has a quinoid structure could absorb longer wavelengths than Ru-1 (Figure S12).
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Supplementary Material

Supporting Information