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Title: CO2 hydrogenation catalyzed by iridium complexes with a proton-responsive ligand

Journal Article · · Inorganic Chemistry
DOI: https://doi.org/10.1021/ic502904q · OSTI ID:1182536
 [1];  [1];  [2];  [2];  [2];  [3];  [3];  [1]
  1. National Institute of Advanced Industrial Science and Technology, Ibaraki (Japan); Japan Science and Technology Agency, Saitama (Japan)
  2. National Institute of Advanced Industrial Science and Technology, Ibaraki (Japan)
  3. Brookhaven National Lab. (BNL), Upton, NY (United States)
+ Show Author Affiliations

In this study, the catalytic cycle for the production of formic acid by CO₂ hydrogenation and the reverse reaction has received renewed attention because they are viewed as offering a viable scheme for hydrogen storage and release. In this Forum Article, CO₂ hydrogenation catalyzed by iridium complexes bearing N^N-bidentate ligands is reported. We describe how a ligand containing hydroxyl groups as proton-responsive substituents enhances catalytic performance by an electronic effect of the oxyanions and a pendent-base effect through secondary coordination sphere interaction. In particular, [(Cp*IrCl)₂(TH2BPM)]Cl₂ (Cp* = pentamethyl cyclopentadienyl, TH2BPM = 4,4',6,6'-tetrahydroxy-2,2'-bipyrimidine) promotes enormously the catalytic hydrogenation of CO₂ by these synergistic effects under atmospheric pressure and at room temperature. Additionally, newly designed complexes with azole-type ligands are applied to CO₂ hydrogenation. The catalytic efficiencies of the azole-type complexes are much higher than that of the unsubstituted bipyridine complex [Cp*Ir(bpy)(OH₂)]SO₄. Furthermore, the introduction of one or more hydroxyl groups into ligands such as 2-pyrazolyl-6-hydroxypyridine, 2-pyrazolyl-4,6-dihydroxyl pyrimidine, and 4-pyrazolyl-2,6-dihydroxyl pyrimidine enhanced catalytic activity. It is clear that the incorporation of electron-donating hydroxyl groups into proton-responsive ligands is effective for promoting the hydrogenation of CO₂.

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:
1182536
Report Number(s):
BNL--107637-2015-JA; KC0304030
Journal Information:
Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 11 Vol. 54; ISSN 0020-1669
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

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Efficient Hydrogen Storage and Production Using a Catalyst with an Imidazoline‐Based, Proton‐Responsive Ligand journal December 2016
Ruthenium NNN complexes with a 2-hydroxypyridylmethylene fragment for transfer hydrogenation of ketones: Ruthenium complexes for transfer hydrogenation of ketones journal October 2017
Base-free hydrogenation of CO 2 to formic acid in water with an iridium complex bearing a N,N′-diimine ligand journal January 2016
Mixed-valence copper( i,ii ) complexes with 4-(1H-pyrazol-1-yl)-6-R-pyrimidines: from ionic structures to coordination polymers journal January 2016
Ruthenium complexes bearing an unsymmetrical pincer ligand with a 2-hydroxypyridylmethylene fragment: active catalysts for transfer hydrogenation of ketones journal January 2016
Half‐sandwich ruthenium complexes with S chiff base ligands bearing a hydroxyl group: Preparation, characterization and catalytic activities journal November 2019
Making a Splash in Homogeneous CO 2 Hydrogenation: Elucidating the Impact of Solvent on Catalytic Mechanisms journal July 2018
Protic NNN and NCN Pincer-Type Ruthenium Complexes Featuring (Trifluoromethyl)pyrazole Arms: Synthesis and Application to Catalytic Hydrogen Evolution from Formic Acid journal December 2017
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Iridium Complexes with Proton-Responsive Azole-Type Ligands as Effective Catalysts for CO 2 Hydrogenation journal November 2017
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Bio-mimetic self-assembled computationally designed catalysts of Mo and W for hydrogenation of CO 2 /dehydrogenation of HCOOH inspired by the active site of formate dehydrogenase journal January 2019
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Biomimetic heterobimetallic architecture of Ni( ii ) and Fe( ii ) for CO 2 hydrogenation in aqueous media. A DFT study journal January 2019
Utilization of a Fluorescent Dye Molecule as a Proton and Electron Reservoir journal February 2018
Iridium–NHC-based catalyst for ambient pressure storage and low temperature release of H 2 via the CO 2 /HCO 2 H couple journal January 2018
A DFT Study of CO2Hydrogenation on Faujasite-Supported Ir4Clusters: on the Role of Water for Selectivity Control journal June 2016
Enhanced Hydrogen Generation from Formic Acid by Half-Sandwich Iridium(III) Complexes with Metal/NH Bifunctionality: A Pronounced Switch from Transfer Hydrogenation journal August 2015
Development of Effective Catalysts for Hydrogen Storage Technology Using Formic Acid journal September 2018
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A computational study on ligand assisted vs. ligand participation mechanisms for CO 2 hydrogenation: importance of bifunctional ligand based catalysts journal January 2019
A Precious Catalyst: Rhodium-Catalyzed Formic Acid Dehydrogenation in Water: A Precious Catalyst: Rhodium-Catalyzed Formic Acid Dehydrogenation in Water journal April 2019
Carbon Nitride as a Ligand: Selective Hydrogenation of Terminal Alkenes Using [(η 5 ‐C 5 Me 5 )IrCl(g‐C 3 N 4 ‐κ 2 N,N’ )]Cl journal April 2020

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
proton-responsive ligand
iridium complexes
CO₂ hydrogenation