Photoinduced Nitrite Reduction to NO: Closing the Cycle with Dinuclear Ruthenium Complexes
The reduction of nitrite to nitric oxide (NO) is a crucial step in the nitrogen cycle, catalyzed by nitrite reductase in nature, and its efficient catalysis is of great interest. This study reports the achievement of a reduction cycle that releases NO from nitrite using a dinuclear ruthenium complex (NO<sub>2</sub> <sup>-</sup> + 2H<sup>+</sup> + e<sup>-</sup> → NO + H<sub>2</sub>O). Irradiation or thermolysis of a nitrite-bridged complex, [(TpRu)<sub>2</sub>(μ-Cl)-(μ-NO<sub>2</sub>)-(μ-pz)] (<b>1</b>) (Tp = HB-(pyrazol-1-yl)<sub>3</sub>), resulted in the formation of an oxido-bridged complex, [(TpRu)<sub>2</sub>(μ-Cl)-(μ-O)-(μ-pz)] (<b>2</b>), and the release of NO. The reaction mechanism from <b>1</b> to <b>2</b> was investigated through theoretical calculations. To complete the reduction cycle, complex <b>1</b> was reproduced from complex <b>2</b> using two protons and one electron in the presence of a nitrite salt. This study demonstrated the successful mimicking of the function of nitrite reductase using a dinuclear ruthenium complex.
Authors
- Kazunari Yoshizawa (ORCID: https://orcid.org/0000-0002-6279-9722)
- Eri Sakuda (ORCID: https://orcid.org/0000-0001-9882-7628)
- Keisuke Umakoshi (ORCID: https://orcid.org/0000-0002-2027-6333)
- Kenichiro Omoto (ORCID: https://orcid.org/0000-0002-4134-3005)
- Yasuhiro Arikawa (ORCID: https://orcid.org/0000-0001-6727-2340)
- Taiji Nakamura (ORCID: https://orcid.org/0000-0002-7301-9752)
- Shintaro Yoshida (ORCID: https://orcid.org/0000-0002-3449-741X)
Institutions
- Kyoto University (JP)
- Nagasaki University (JP)
Publication Details
- Journal
- ACS Omega
- Published
- 2025-06-24
- DOI
- https://doi.org/10.1021/acsomega.5c02559
- Primary Topic
- Ammonia Synthesis and Nitrogen Reduction
- Type
- article
- Field-Weighted Citation Impact
- 0.00
Funders
- Naito Foundation
- Japan Society for the Promotion of Science