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Download Hi-Res ImageDownload to MS-PowerPointCite This:Inorg. Chem. 2019, 58, 11, 7274-7284
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Dual Catalytic Cycle of H2 and H2O Oxidations by a Half-Sandwich Iridium Complex: A Theoretical Study

  • Kei Ikeda
    Kei Ikeda
    Department of Chemistry and Biochemistry, Graduate School of Engineering, Kyushu University, Fukuoka 819-0395, Japan
    More by Kei Ikeda
    • , 
  • Yuta Hori
    Yuta Hori
    Institute for Materials Chemistry and Engineering, Kyushu University, Fukuoka 819-0395, Japan
    More by Yuta Hori
    • , 
  • Muhammad Haris Mahyuddin
    Muhammad Haris Mahyuddin
    Institute for Materials Chemistry and Engineering, Kyushu University, Fukuoka 819-0395, Japan
    More by Muhammad Haris Mahyuddin
    Orcidhttp://orcid.org/0000-0002-8017-7847
    • , 
  • Yoshihito Shiota
    Yoshihito Shiota
    Institute for Materials Chemistry and Engineering, Kyushu University, Fukuoka 819-0395, Japan
    More by Yoshihito Shiota
    • , 
  • Aleksandar Staykov
    Aleksandar Staykov
    International Institute for Carbon-Neutral Energy Research (WPI-I2CNER), Kyushu University, Fukuoka 819-0395, Japan
    More by Aleksandar Staykov
    • , 
  • Takahiro Matsumoto
    Takahiro Matsumoto
    Department of Chemistry and Biochemistry, Graduate School of Engineering, Kyushu University, Fukuoka 819-0395, Japan
    International Institute for Carbon-Neutral Energy Research (WPI-I2CNER), Kyushu University, Fukuoka 819-0395, Japan
    Center for Small Molecule Energy, Kyushu University, Fukuoka 819-0395, Japan
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    • , 
  • Kazunari Yoshizawa*
    Kazunari Yoshizawa
    Institute for Materials Chemistry and Engineering, Kyushu University, Fukuoka 819-0395, Japan
    *(K.Y.) E-mail: [email protected]
    More by Kazunari Yoshizawa
    Orcidhttp://orcid.org/0000-0002-6279-9722
    • , and 
  • Seiji Ogo*
    Seiji Ogo
    Department of Chemistry and Biochemistry, Graduate School of Engineering, Kyushu University, Fukuoka 819-0395, Japan
    International Institute for Carbon-Neutral Energy Research (WPI-I2CNER), Kyushu University, Fukuoka 819-0395, Japan
    Center for Small Molecule Energy, Kyushu University, Fukuoka 819-0395, Japan
    *(S.O.) E-mail: [email protected]
    More by Seiji Ogo
    Orcidhttp://orcid.org/0000-0003-2078-6349
Cite this: Inorg. Chem. 2019, 58, 11, 7274–7284
Publication Date (Web):May 16, 2019
https://doi.org/10.1021/acs.inorgchem.9b00307
Copyright © 2019 American Chemical Society
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Abstract

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While hydrogenase and photosystem II enzymes are known to oxidize H2 and H2O, respectively, a recently reported iridium aqua complex [IrIII(η5-C5Me5){bpy(COOH)2}(H2O)]2+ is able to oxidize both of the molecules and generate energies as in the fuel and solar cells (Ogo ChemCatChem 2017, 9, 4024−4028). To understand the mechanism behind such an interesting bifunctional catalyst, in the present study, we perform density functional theory (DFT) calculations on the dual catalytic cycle of H2 and H2O oxidations by the iridium aqua complex. In the H2 oxidation, we found that the H–H bond is easily cleaved in a heterolytic fashion, and the resultant iridium hydride complex is significantly stabilized by the presence of H2O molecules, due to dihydrogen bond. The rate-determining step of this reaction is found to be the H2O → H2 ligand substitution with an activation energy of 10.7 kcal/mol. In the H2O oxidation, an iridium oxo complex originating from an oxidation of the iridium aqua complex forms a hydroperoxide complex, where an O–O bond is formed with an activation energy of 21.0 kcal/mol. Such a relatively low activation barrier is possible only when at least two H2O molecules are present in the reaction, allowing the water nucleophilic attack (WNA) mechanism to take place. The present study suggests and discusses in detail six reaction steps required for the dual catalytic cycle to complete.

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The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.inorgchem.9b00307.

  • Descriptions, energy diagrams, optimized structures, natural populations, and spin densities of the A3, B2, and B3 processes and Cartesian coordinates for all optimized structures (PDF)

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Cited By

This article is cited by 2 publications.

  1. Kei Ikeda, Muhammad Haris Mahyuddin, Yoshihito Shiota, Kazunari Yoshizawa. Active Catalyst for Methane Hydroxylation by an Iridium–Oxo Complex. ACS Catalysis 2020, 10 (15) , 8254-8262. https://doi.org/10.1021/acscatal.0c01610
  2. Kei Ikeda, Muhammad Haris Mahyuddin, Yoshihito Shiota, Aleksandar Staykov, Takahiro Matsumoto, Seiji Ogo, Kazunari Yoshizawa. Computational Study on the Light-Induced Oxidation of Iridium–Aqua Complex to Iridium–Oxo Complex over WO3(001) Surface. Inorganic Chemistry 2020, 59 (1) , 415-422. https://doi.org/10.1021/acs.inorgchem.9b02704

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