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Efficient Iridium Catalysts for Formic Acid Dehydrogenation: Investigating the Electronic Effect on the Elementary β-Hydride Elimination and Hydrogen Formation Steps

Journal Article · · Inorganic Chemistry
 [1];  [2];  [1];  [3];  [3];  [2];  [1]
  1. Dalian Univ. of Technology (China); Southern University of Science and Technology, Shenzhen, Guangdong (China)
  2. Dalian Univ. of Technology (China)
  3. Brookhaven National Lab. (BNL), Upton, NY (United States)
+ Show Author Affiliations
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.
Research Organization:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
SC0012704
OSTI ID:
1784494
Report Number(s):
BNL--221390-2021-JAAM
Journal Information:
Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 5 Vol. 60; ISSN 0020-1669
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
dehydrogenation
formic acid
homogeneous catalysis
iridium complex
substituent effects