Citation: Huihua GONG, Tianhua CUI, Li JI, Jichuan ZHANG, Liyuan ZHANG, Yan CHEN, Zhenye WANG, Jiaqi XU, Ruixiang LI. Hydrogenation of CO₂ to formate catalyzed by N-heterocyclic carbene-nitrogen-phosphine chelated iridium(Ⅰ) complexes[J]. Chinese Journal of Inorganic Chemistry, ;2025, 41(12): 2609-2620. doi: 10.11862/CJIC.20250170 shu

Hydrogenation of CO₂ to formate catalyzed by N-heterocyclic carbene-nitrogen-phosphine chelated iridium(Ⅰ) complexes

Huihua GONG ^{1, 2} ,
Tianhua CUI ³ ,
Li JI ⁴ ,
Jichuan ZHANG ¹ ,
Liyuan ZHANG ^{1, 5} ,
Yan CHEN ¹ ,
Zhenye WANG ¹ ,
Jiaqi XU ^2,, ,
Ruixiang LI ^2,,

1.
Analytical and Testing Center, College of Chemistry and Environmental Engineering, Neijiang Normal University, Neijiang, Sichuan 641112, China
2.
Key Laboratory of Green Chemistry and Technology of Ministry of Education, College of Chemistry, Sichuan University, Chengdu 610064, China
3.
Shaanxi Hydrogen Energy Research Institute Co., Ltd., Xi′an 712046, China
4.
Sichuan Research Institute of Chemical Quality and Safety Testing, Chengdu 610031, China
5.
Special Agricultural Resources in Tuojiang River Basin Sharing and Service Platform of Sichuan Province, Neijiang, Sichuan 641112, China

Corresponding author: Jiaqi XU, jqxu@scu.edu.cn Ruixiang LI, liruixiang@scu.edu.cn
Received Date: 23 May 2025
Revised Date: 24 September 2025

Figures(6)

To achieve efficient catalytic hydrogenation of CO₂ to formate, we employed a transmetallation strategy to develop three novel iridium(Ⅰ) complexes, which feature N-heterocyclic carbene-nitrogen-phosphine ligands (CNP) and a 1, 5-cyclooctadiene (cod) molecule: [Ir(cod)(κ³-CN^imP)]Cl (1-Cl), [Ir(cod)(κ³-CN^imP)]PF₆ (1-PF₆), and [Ir(cod)(κ³-CN^HP)]Cl (2). The ¹H NMR spectra, ³¹P NMR spectra, and high-resolution mass spectra verify the successful synthesis of these three Ir(Ⅰ)-CNP complexes. Furthermore, single-crystal X-ray diffraction analysis confirms the coordination geometry of 1-PF₆. The strong Ir—C(NHC) bond suggests that the carbene carbon plays an enhanced anchoring role to iridium due to its strong σ-donating ability, which helps stabilize the active metal species during CO₂ hydrogenation. As a result, the Ir(Ⅰ)-CNP complex exhibits remarkable activity and long catalytic lifetime for the hydrogenation of CO₂ to formate, reaching a turnover number (TON) of 1.16×10⁶ after 150 h at a high temperature of 170 ℃, which was a relatively high value among all the Ir complexes.
- CO₂ hydrogenation,
- iridium complex,
- CNP ligands,
- homogeneous catalysis
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Hydrogenation of CO2 to formate catalyzed by N-heterocyclic carbene-nitrogen-phosphine chelated iridium(Ⅰ) complexes

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通讯作者: 陈斌, bchen63@163.com

Hydrogenation of CO₂ to formate catalyzed by N-heterocyclic carbene-nitrogen-phosphine chelated iridium(Ⅰ) complexes