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Title: Striking differences in properties of geometric isomers of [Ir(tpy)(ppy)H](+): Experimental and computational studies on their hydricities, interaction with CO2, and photochemistry

Abstract

Here, we prepared two geometric isomers of [Ir(tpy)(ppy)H]+, previously proposed as a key intermediate in the photochemical reduction of CO2 to CO, and characterized their notably different ground- and excited-state interactions with CO2 and their hydricities using experimental and computational methods. Only one isomer, C-trans-[Ir(tpy)(ppy)H]+, reacts with CO2 to generate the formato complex in the ground state, consistent with its calculated hydricity. Under photocatalytic conditions in CH3CN/TEOA, a common reactive C-trans-[Ir(tpy)(ppy)]0 species, irrespective of the starting isomer or monodentate ligand (such as hydride or Cl), reacts with CO2 and produces CO with the same catalytic efficiency.

Authors:
 [1];  [1];  [2];  [1];  [3];  [4];  [5];  [1]
  1. Brookhaven National Lab. (BNL), Upton, NY (United States)
  2. Brookhaven National Lab. (BNL), Upton, NY (United States); PRESTO, Saitama (Japan); Kanagawa Univ., Yokohama (Japan)
  3. Brookhaven National Lab. (BNL), Upton, NY (United States); Adam Mickiewicz Univ., Poznan (Poland)
  4. PRESTO, Saitama (Japan); Toyota Central R&D Labs., Inc., Aichi (Japan)
  5. Baruch College, CUNY, New York, NY (United States)
Publication Date:
Research Org.:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1263904
Report Number(s):
BNL-111788-2016-JA
Journal ID: ISSN 1433-7851; R&D Project: CO026; KC0304030
Grant/Contract Number:  
SC00112704
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Angewandte Chemie (International Edition)
Additional Journal Information:
Journal Volume: 54; Journal Issue: 47; Journal ID: ISSN 1433-7851
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; CO2 reduction; homogeneous catalysis; hydricity; iridium hydrides; photochemistry

Citation Formats

Garg, Komal, Fujita, Etsuko, Matsubara, Yasuo, Ertem, Mehmed Z., Lewandowska-Andralojc, Anna, Sato, Shunsuke, Szalda, David J., and Muckerman, James T. Striking differences in properties of geometric isomers of [Ir(tpy)(ppy)H](+): Experimental and computational studies on their hydricities, interaction with CO2, and photochemistry. United States: N. p., 2015. Web. doi:10.1002/anie.201506961.
Garg, Komal, Fujita, Etsuko, Matsubara, Yasuo, Ertem, Mehmed Z., Lewandowska-Andralojc, Anna, Sato, Shunsuke, Szalda, David J., & Muckerman, James T. Striking differences in properties of geometric isomers of [Ir(tpy)(ppy)H](+): Experimental and computational studies on their hydricities, interaction with CO2, and photochemistry. United States. https://doi.org/10.1002/anie.201506961
Garg, Komal, Fujita, Etsuko, Matsubara, Yasuo, Ertem, Mehmed Z., Lewandowska-Andralojc, Anna, Sato, Shunsuke, Szalda, David J., and Muckerman, James T. 2015. "Striking differences in properties of geometric isomers of [Ir(tpy)(ppy)H](+): Experimental and computational studies on their hydricities, interaction with CO2, and photochemistry". United States. https://doi.org/10.1002/anie.201506961. https://www.osti.gov/servlets/purl/1263904.
@article{osti_1263904,
title = {Striking differences in properties of geometric isomers of [Ir(tpy)(ppy)H](+): Experimental and computational studies on their hydricities, interaction with CO2, and photochemistry},
author = {Garg, Komal and Fujita, Etsuko and Matsubara, Yasuo and Ertem, Mehmed Z. and Lewandowska-Andralojc, Anna and Sato, Shunsuke and Szalda, David J. and Muckerman, James T.},
abstractNote = {Here, we prepared two geometric isomers of [Ir(tpy)(ppy)H]+, previously proposed as a key intermediate in the photochemical reduction of CO2 to CO, and characterized their notably different ground- and excited-state interactions with CO2 and their hydricities using experimental and computational methods. Only one isomer, C-trans-[Ir(tpy)(ppy)H]+, reacts with CO2 to generate the formato complex in the ground state, consistent with its calculated hydricity. Under photocatalytic conditions in CH3CN/TEOA, a common reactive C-trans-[Ir(tpy)(ppy)]0 species, irrespective of the starting isomer or monodentate ligand (such as hydride or Cl), reacts with CO2 and produces CO with the same catalytic efficiency.},
doi = {10.1002/anie.201506961},
url = {https://www.osti.gov/biblio/1263904}, journal = {Angewandte Chemie (International Edition)},
issn = {1433-7851},
number = 47,
volume = 54,
place = {United States},
year = {Mon Nov 16 00:00:00 EST 2015},
month = {Mon Nov 16 00:00:00 EST 2015}
}

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Works referenced in this record:

Excited-State Deprotonation and H/D Exchange of an Iridium Hydride Complex
journal, November 2003


Photoswitchable Hydride Transfer from Iridium to 1-Methylnicotinamide Rationalized by Thermochemical Cycles
journal, October 2014


Rapid Transfer of Hydride Ion from a Ruthenium Complex to C 1 Species in Water
journal, August 2007


Calculation of thermodynamic hydricities and the design of hydride donors for CO2 reduction
journal, July 2012


Thermodynamic and Kinetic Hydricity of Ruthenium(II) Hydride Complexes
journal, September 2012


Excited-State Deprotonation and H/D Exchange of an Iridium Hydride Complex
journal, November 2003


Artificial Photosynthesis and Solar Fuels
journal, December 2009


Molecular artificial photosynthesis
journal, January 2014


Development of Molecular Electrocatalysts for CO2 Reduction and H2 Production/Oxidation
journal, December 2009


Evidence for strong mixing between the LC and MLCT excited states in bis(2-phenylpyridinato-C2,N')(2,2'-bipyridine)iridium(III)
journal, July 1993


Syntheses and Properties of Emissive Iridium(III) Complexes with Tridentate Benzimidazole Derivatives
journal, June 2005


Hydride Donor Abilities and Bond Dissociation Free Energies of Transition Metal Formyl Complexes
journal, March 2002


Photochemical carbon dioxide reduction with metal complexes
journal, May 1999


A Highly Efficient Mononuclear Iridium Complex Photocatalyst for CO 2 Reduction under Visible Light
journal, November 2012


Molecular Approaches to the Photocatalytic Reduction of Carbon Dioxide for Solar Fuels
journal, December 2009


A Highly Efficient Mononuclear Iridium Complex Photocatalyst for CO 2 Reduction under Visible Light
journal, November 2012


Artificial Photosynthesis and Solar Fuels
book, March 2021


Works referencing / citing this record:

Photochemically Driven Reverse Water-Gas Shift at Ambient Conditions mediated by a Nickel Pincer Complex
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Judicious Ligand Design in Ruthenium Polypyridyl CO 2 Reduction Catalysts to Enhance Reactivity by Steric and Electronic Effects
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The elusive abnormal CO2 insertion enabled by metal-ligand cooperative photochemical selectivity inversion
journal, March 2018


Hydricity, electrochemistry, and excited-state chemistry of Ir complexes for CO 2 reduction
journal, January 2017


A hexanuclear cobalt metal–organic framework for efficient CO 2 reduction under visible light
journal, January 2017


Photochemically Driven Reverse Water-Gas Shift at Ambient Conditions mediated by a Nickel Pincer Complex
journal, July 2018


Nickel Complexes of C-Substituted Cyclams and Their Activity for CO2 and H+ Reduction
journal, July 2017