Efficient Iridium Catalysts for Formic Acid Dehydrogenation: Investigating the Electronic Effect on the Elementary β-Hydride Elimination and Hydrogen Formation Steps
Abstract
We report herein a series of Cp*Ir complexes containing a rigid 8-aminoquinolinesulfonamide moiety as highly efficient catalysts for the dehydrogenation of formic acid (FA). The complex [Cp*Ir(L)Cl] (HL = N-(quinolin-8-yl)benzenesulfonamide) displayed a high turnover frequency (TOF) of 2.97 × 104 h–1 and a good stability (>100 h) at 60 °C. Comparative studies of [Cp*Ir(L)Cl] with the rigid ligand and [Cp*Ir(L')Cl] (HL' = N-propylpypridine-2-sulfonamide) without the rigid aminoquinoline moiety demonstrated that the 8-aminoquinoline moiety could dramatically enhance the stability of the catalyst. The electron-donating ability of the N,N'-chelating ligand was tuned by functionalizing the phenyl group of the L ligand with OMe, Cl, and CF3 to have a systematical perturbation of the electronic structure of [Cp*Ir(L)Cl]. Experimental kinetic studies and density functional theory (DFT) calculations on this series of Cp*Ir complexes revealed that (i) the electron-donating groups enhance the hydrogen formation step while slowing down the β-hydride elimination and (ii) the electron-withdrawing groups display the opposite effect on these reaction steps, which in turn leads to lower optimum pH for catalytic activity compared to the electron-donating groups.
- Authors:
-
[2];
[3];
[3];
[2];
[1]
- Dalian Univ. of Technology (China); Southern University of Science and Technology, Shenzhen, Guangdong (China)
- Dalian Univ. of Technology (China)
- Brookhaven National Lab. (BNL), Upton, NY (United States)
- Publication Date:
- Research Org.:
- Brookhaven National Lab. (BNL), Upton, NY (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1784494
- Report Number(s):
- BNL-221390-2021-JAAM
Journal ID: ISSN 0020-1669
- Grant/Contract Number:
- SC0012704
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Inorganic Chemistry
- Additional Journal Information:
- Journal Volume: 60; Journal Issue: 5; Journal ID: ISSN 0020-1669
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; formic acid; dehydrogenation; iridium complex; homogeneous catalysis; substituent effects
Citation Formats
Liu, Hong, Wang, Wan-Hui, Xiong, Huatian, Nijamudheen, A., Ertem, Mehmed Z., Wang, Mei, and Duan, Lele. Efficient Iridium Catalysts for Formic Acid Dehydrogenation: Investigating the Electronic Effect on the Elementary β-Hydride Elimination and Hydrogen Formation Steps. United States: N. p., 2021.
Web. doi:10.1021/acs.inorgchem.0c03815.
Liu, Hong, Wang, Wan-Hui, Xiong, Huatian, Nijamudheen, A., Ertem, Mehmed Z., Wang, Mei, & Duan, Lele. Efficient Iridium Catalysts for Formic Acid Dehydrogenation: Investigating the Electronic Effect on the Elementary β-Hydride Elimination and Hydrogen Formation Steps. United States. https://doi.org/10.1021/acs.inorgchem.0c03815
Liu, Hong, Wang, Wan-Hui, Xiong, Huatian, Nijamudheen, A., Ertem, Mehmed Z., Wang, Mei, and Duan, Lele. Tue .
"Efficient Iridium Catalysts for Formic Acid Dehydrogenation: Investigating the Electronic Effect on the Elementary β-Hydride Elimination and Hydrogen Formation Steps". United States. https://doi.org/10.1021/acs.inorgchem.0c03815. https://www.osti.gov/servlets/purl/1784494.
@article{osti_1784494,
title = {Efficient Iridium Catalysts for Formic Acid Dehydrogenation: Investigating the Electronic Effect on the Elementary β-Hydride Elimination and Hydrogen Formation Steps},
author = {Liu, Hong and Wang, Wan-Hui and Xiong, Huatian and Nijamudheen, A. and Ertem, Mehmed Z. and Wang, Mei and Duan, Lele},
abstractNote = {We report herein a series of Cp*Ir complexes containing a rigid 8-aminoquinolinesulfonamide moiety as highly efficient catalysts for the dehydrogenation of formic acid (FA). The complex [Cp*Ir(L)Cl] (HL = N-(quinolin-8-yl)benzenesulfonamide) displayed a high turnover frequency (TOF) of 2.97 × 104 h–1 and a good stability (>100 h) at 60 °C. Comparative studies of [Cp*Ir(L)Cl] with the rigid ligand and [Cp*Ir(L')Cl] (HL' = N-propylpypridine-2-sulfonamide) without the rigid aminoquinoline moiety demonstrated that the 8-aminoquinoline moiety could dramatically enhance the stability of the catalyst. The electron-donating ability of the N,N'-chelating ligand was tuned by functionalizing the phenyl group of the L ligand with OMe, Cl, and CF3 to have a systematical perturbation of the electronic structure of [Cp*Ir(L)Cl]. Experimental kinetic studies and density functional theory (DFT) calculations on this series of Cp*Ir complexes revealed that (i) the electron-donating groups enhance the hydrogen formation step while slowing down the β-hydride elimination and (ii) the electron-withdrawing groups display the opposite effect on these reaction steps, which in turn leads to lower optimum pH for catalytic activity compared to the electron-donating groups.},
doi = {10.1021/acs.inorgchem.0c03815},
journal = {Inorganic Chemistry},
number = 5,
volume = 60,
place = {United States},
year = {Tue Feb 09 00:00:00 EST 2021},
month = {Tue Feb 09 00:00:00 EST 2021}
}
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