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Title: Efficient Cp*Ir Catalysts with Imidazoline Ligands for CO 2 Hydrogenation: Cp*Ir Catalysts with Imidazoline Ligands for CO 2 Hydrogenation

Journal Article · · European Journal of Inorganic Chemistry
 [1];  [1];  [1];  [1];  [2];  [3];  [3];  [1]
  1. National Inst. of Advanced Industrial Science and Technology (AIST), Tsukuba (Japan)
  2. Dalian Univ. of Technology, Panjin (China). School of Petroleum and Chemical Engineering
  3. Brookhaven National Lab. (BNL), Upton, NY (United States). Chemistry Dept.
+ Show Author Affiliations

Here, we report newly developed iridium catalysts with electron-donating imidazoline moieties as ligands for the hydrogenation of CO2 to formate in aqueous solution. Interestingly, these new complexes promote CO2 hydrogenation much more effectively than their imidazole analogues and exhibit a turnover frequency (TOF) of 1290 h–1 for the bisimidazoline complex compared to that of 20 h–1 for the bisimidazole complex at 1 MPa and 50 °C. Additionally, the hydrogenation proceeds smoothly even under atmospheric pressure at room temperature. The TOF of 43 h–1 for the bisimidazoline complex is comparable to that of a dinuclear complex (70 h–1, highest TOF reported) [Nat. Chem. 2012, 4, 383], which incorporates proton-responsive ligands with pendent-OH groups in the second coordination sphere. The catalytic activity of the complex with an N-methylated imidazoline moiety is much the same as that of the corresponding pyridylimidazoline analogue. Our result and the UV/Vis titrations of the imidazoline complexes indicate that the high activity is not attributable to the deprotonation of NH on the imidazoline under the reaction conditions.

Research Organization:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI ID:
1335387
Report Number(s):
BNL--111790-2016-JA; KC0304030
Journal Information:
European Journal of Inorganic Chemistry, Journal Name: European Journal of Inorganic Chemistry Journal Issue: 34 Vol. 2015; ISSN 1434-1948
Publisher:
ChemPubSoc EuropeCopyright Statement
Country of Publication:
United States
Language:
English

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Cited By (12)

Carbon Dioxide Hydrogenation and Formic Acid Dehydrogenation Catalyzed by Iridium Complexes Bearing Pyridyl-pyrazole Ligands: Effect of an Electron-donating Substituent on the Pyrazole Ring on the Catalytic Activity and Durability journal November 2018
Development of Effective Catalysts for Hydrogen Storage Technology Using Formic Acid journal September 2018
Ligand Effect on the Stability of Water‐Soluble Iridium Catalysts for High‐Pressure Hydrogen Gas Production by Dehydrogenation of Formic Acid journal March 2019
Ligand Effect on the Stability of Water‐Soluble Iridium Catalysts for High‐Pressure Hydrogen Gas Production by Dehydrogenation of Formic Acid journal March 2019
Efficient Hydrogen Storage and Production Using a Catalyst with an Imidazoline‐Based, Proton‐Responsive Ligand journal December 2016
Iridium Complexes with Proton-Responsive Azole-Type Ligands as Effective Catalysts for CO 2 Hydrogenation journal November 2017
A Precious Catalyst: Rhodium-Catalyzed Formic Acid Dehydrogenation in Water: A Precious Catalyst: Rhodium-Catalyzed Formic Acid Dehydrogenation in Water journal April 2019
Base-free hydrogenation of CO 2 to formic acid in water with an iridium complex bearing a N,N′-diimine ligand journal January 2016
New Ru( ii ) N′NN′-type pincer complexes: synthesis, characterization and the catalytic hydrogenation of CO 2 or bicarbonates to formate salts journal January 2017
Conversion of CO 2 from air into formate using amines and phosphorus-nitrogen PN 3 P-Ru( ii ) pincer complexes journal January 2018
Sequential hydrogen production system from formic acid and H 2 /CO 2 separation under high-pressure conditions journal January 2018
CO 2 hydrogenation by phosphorus–nitrogen PN 3 P-pincer iridium hydride complexes: elucidation of the deactivation pathway journal January 2019

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
CO2 hydrogenation
Ir complex
homogeneous catalysis