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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

Abstract

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.

Authors:
 [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.
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:
1335387
Report Number(s):
BNL-111790-2016-JA
Journal ID: ISSN 1434-1948; R&D Project: CO026; KC0304030
Grant/Contract Number:  
SC00112704
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
European Journal of Inorganic Chemistry
Additional Journal Information:
Journal Volume: 2015; Journal Issue: 34; Journal ID: ISSN 1434-1948
Publisher:
ChemPubSoc Europe
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; homogeneous catalysis; Ir complex; CO2 hydrogenation

Citation Formats

Xu, Shaoan, Onishi, Naoya, Tsurusaki, Akihiro, Manaka, Yuichi, Wang, Wan-Hui, Muckerman, James T., Fujita, Etsuko, and Himeda, Yuichiro. Efficient Cp*Ir Catalysts with Imidazoline Ligands for CO 2 Hydrogenation: Cp*Ir Catalysts with Imidazoline Ligands for CO 2 Hydrogenation. United States: N. p., 2015. Web. doi:10.1002/ejic.201501030.
Xu, Shaoan, Onishi, Naoya, Tsurusaki, Akihiro, Manaka, Yuichi, Wang, Wan-Hui, Muckerman, James T., Fujita, Etsuko, & Himeda, Yuichiro. Efficient Cp*Ir Catalysts with Imidazoline Ligands for CO 2 Hydrogenation: Cp*Ir Catalysts with Imidazoline Ligands for CO 2 Hydrogenation. United States. https://doi.org/10.1002/ejic.201501030
Xu, Shaoan, Onishi, Naoya, Tsurusaki, Akihiro, Manaka, Yuichi, Wang, Wan-Hui, Muckerman, James T., Fujita, Etsuko, and Himeda, Yuichiro. 2015. "Efficient Cp*Ir Catalysts with Imidazoline Ligands for CO 2 Hydrogenation: Cp*Ir Catalysts with Imidazoline Ligands for CO 2 Hydrogenation". United States. https://doi.org/10.1002/ejic.201501030. https://www.osti.gov/servlets/purl/1335387.
@article{osti_1335387,
title = {Efficient Cp*Ir Catalysts with Imidazoline Ligands for CO 2 Hydrogenation: Cp*Ir Catalysts with Imidazoline Ligands for CO 2 Hydrogenation},
author = {Xu, Shaoan and Onishi, Naoya and Tsurusaki, Akihiro and Manaka, Yuichi and Wang, Wan-Hui and Muckerman, James T. and Fujita, Etsuko and Himeda, Yuichiro},
abstractNote = {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.},
doi = {10.1002/ejic.201501030},
url = {https://www.osti.gov/biblio/1335387}, journal = {European Journal of Inorganic Chemistry},
issn = {1434-1948},
number = 34,
volume = 2015,
place = {United States},
year = {Mon Nov 09 00:00:00 EST 2015},
month = {Mon Nov 09 00:00:00 EST 2015}
}

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Works referenced in this record:

Liquid organic and inorganic chemical hydrides for high-capacity hydrogen storage
journal, January 2015


Use of carbon dioxide in energy storage
journal, September 1978


Preface for Small-Molecule Activation: Carbon-Containing Fuels
journal, May 2015


Well-Defined Iron Catalyst for Improved Hydrogenation of Carbon Dioxide and Bicarbonate
journal, December 2012


Iron catalyzed CO 2 hydrogenation to formate enhanced by Lewis acid co-catalysts
journal, January 2015


Iron-Catalyzed Hydrogenation of Bicarbonates and Carbon Dioxide to Formates
journal, January 2015


Hydricity of an Fe–H Species and Catalytic CO 2 Hydrogenation
journal, December 2014


Homogeneous catalytic hydrogenation of supercritical carbon dioxide
journal, March 1994


A Charge/Discharge Device for Chemical Hydrogen Storage and Generation
journal, September 2011


Ruthenium(II)Phosphite Complexes as Catalysts for the Hydrogenation of Carbon Dioxide
journal, February 2013


Highly Efficient Reversible Hydrogenation of Carbon Dioxide to Formates Using a Ruthenium PNP-Pincer Catalyst
journal, April 2014


Direct synthesis of formic acid from carbon dioxide by hydrogenation in acidic media
journal, June 2014


Amine-Free Reversible Hydrogen Storage in Formate Salts Catalyzed by Ruthenium Pincer Complex without pH Control or Solvent Change
journal, March 2015


Catalytic CO 2 Hydrogenation to Formate by a Ruthenium Pincer Complex
journal, September 2013


Hydrogenation of Carbon Dioxide to Formate Catalyzed by a Copper/1,8-Diazabicyclo[5.4.0]undec-7-ene System
journal, April 2015


Cp*Co(III) Catalysts with Proton-Responsive Ligands for Carbon Dioxide Hydrogenation in Aqueous Media
journal, October 2013


A Cobalt Hydride Catalyst for the Hydrogenation of CO 2 : Pathways for Catalysis and Deactivation
journal, September 2014


(Pentamethylcyclopentadienyl)iridium-PTA (PTA = 1,3,5-Triaza-7-phosphaadamantane) Complexes and Their Application in Catalytic Water Phase Carbon Dioxide Hydrogenation
journal, February 2008


Secondary Coordination Sphere Interactions Facilitate the Insertion Step in an Iridium(III) CO 2 Reduction Catalyst
journal, June 2011


Catalytic Hydrogenation of Carbon Dioxide Using Ir(III)−Pincer Complexes
journal, October 2009


‘(η6-arene)Ru(bis-NHC)’ complexes for the reduction of CO2 to formate with hydrogen and by transfer hydrogenation with iPrOH
journal, January 2010


Positional Effects of Hydroxy Groups on Catalytic Activity of Proton-Responsive Half-Sandwich Cp*Iridium(III) Complexes
journal, November 2014


Reversible hydrogen storage using CO2 and a proton-switchable iridium catalyst in aqueous media under mild temperatures and pressures
journal, March 2012


Catalytic interconversion between hydrogen and formic acid at ambient temperature and pressure
journal, January 2012


Simultaneous Tuning of Activity and Water Solubility of Complex Catalysts by Acid−Base Equilibrium of Ligands for Conversion of Carbon Dioxide
journal, January 2007


CO 2 Hydrogenation Catalyzed by Iridium Complexes with a Proton-Responsive Ligand
journal, February 2015


Efficient H 2 generation from formic acid using azole complexes in water
journal, January 2014


Works referencing / citing this record:

Development of Effective Catalysts for Hydrogen Storage Technology Using Formic Acid
journal, September 2018


Iridium Complexes with Proton-Responsive Azole-Type Ligands as Effective Catalysts for CO 2 Hydrogenation
journal, November 2017


Conversion of CO 2 from air into formate using amines and phosphorus-nitrogen PN 3 P-Ru( ii ) pincer complexes
journal, January 2018