skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Mechanism of water oxidation by [Ru(bda)(L)₂]: The return of the "blue dimer"

Abstract

We describe here a combined solution-surface-DFT calculations study for complexes of the type [Ru(bda)(L)₂] including X-ray structure of intermediates, their reactivity, as well as pH-dependent electrochemistry and spectroelectrochemistry. These studies shed light on the mechanism of water oxidation by [Ru(bda)(L)₂], revealing key features unavailable from solution studies with sacrificial oxidants.

Authors:
 [1];  [1];  [2];  [1];  [1]
  1. Brookhaven National Lab. (BNL), Upton, NY (United States)
  2. Baruch College, New York, NY (United States)
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1183859
Report Number(s):
BNL-107984-2015-JA
Journal ID: ISSN 1359-7345; CHCOFS; R&D Project: CO026; KC0304030
Grant/Contract Number:  
SC00112704
Resource Type:
Accepted Manuscript
Journal Name:
ChemComm
Additional Journal Information:
Journal Volume: 51; Journal Issue: 19; Journal ID: ISSN 1359-7345
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Concepcion, Javier J., Zhong, Diane K., Szalda, David J., Muckerman, James T., and Fujita, Etsuko. Mechanism of water oxidation by [Ru(bda)(L)₂]: The return of the "blue dimer". United States: N. p., 2015. Web. doi:10.1039/c4cc07968j.
Concepcion, Javier J., Zhong, Diane K., Szalda, David J., Muckerman, James T., & Fujita, Etsuko. Mechanism of water oxidation by [Ru(bda)(L)₂]: The return of the "blue dimer". United States. doi:10.1039/c4cc07968j.
Concepcion, Javier J., Zhong, Diane K., Szalda, David J., Muckerman, James T., and Fujita, Etsuko. Thu . "Mechanism of water oxidation by [Ru(bda)(L)₂]: The return of the "blue dimer"". United States. doi:10.1039/c4cc07968j. https://www.osti.gov/servlets/purl/1183859.
@article{osti_1183859,
title = {Mechanism of water oxidation by [Ru(bda)(L)₂]: The return of the "blue dimer"},
author = {Concepcion, Javier J. and Zhong, Diane K. and Szalda, David J. and Muckerman, James T. and Fujita, Etsuko},
abstractNote = {We describe here a combined solution-surface-DFT calculations study for complexes of the type [Ru(bda)(L)₂] including X-ray structure of intermediates, their reactivity, as well as pH-dependent electrochemistry and spectroelectrochemistry. These studies shed light on the mechanism of water oxidation by [Ru(bda)(L)₂], revealing key features unavailable from solution studies with sacrificial oxidants.},
doi = {10.1039/c4cc07968j},
journal = {ChemComm},
number = 19,
volume = 51,
place = {United States},
year = {2015},
month = {2}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 23 works
Citation information provided by
Web of Science

Figures / Tables:

Chart 1.A Chart 1.A: Structures of [RuII(bda)(L)2] (L = pic, isq, and P2-py). See ESI for synthetic details.

Save / Share:

Works referenced in this record:

Single-Site, Catalytic Water Oxidation on Oxide Surfaces
journal, November 2009

  • Chen, Zuofeng; Concepcion, Javier J.; Jurss, Jonah W.
  • Journal of the American Chemical Society, Vol. 131, Issue 43, p. 15580-15581
  • DOI: 10.1021/ja906391w

Concerted O atom-proton transfer in the O--O bond forming step in water oxidation
journal, April 2010

  • Chen, Z.; Concepcion, J. J.; Hu, X.
  • Proceedings of the National Academy of Sciences, Vol. 107, Issue 16, p. 7225-7229
  • DOI: 10.1073/pnas.1001132107

Catalytic oxidation of water by an oxo-bridged ruthenium dimer
journal, July 1982

  • Gersten, Susan W.; Samuels, George J.; Meyer, Thomas J.
  • Journal of the American Chemical Society, Vol. 104, Issue 14
  • DOI: 10.1021/ja00378a053

Mechanism of Water Oxidation by Single-Site Ruthenium Complex Catalysts
journal, February 2010

  • Concepcion, Javier J.; Tsai, Ming-Kang; Muckerman, James T.
  • Journal of the American Chemical Society, Vol. 132, Issue 5, p. 1545-1557
  • DOI: 10.1021/ja904906v

Application of High Surface Area Tin-Doped Indium Oxide Nanoparticle Films as Transparent Conducting Electrodes
journal, September 2010

  • Hoertz, Paul G.; Chen, Zuofeng; Kent, Caleb A.
  • Inorganic Chemistry, Vol. 49, Issue 18
  • DOI: 10.1021/ic100719r

Low-Overpotential Water Oxidation by a Surface-Bound Ruthenium-Chromophore-Ruthenium-Catalyst Assembly
journal, November 2013

  • Norris, Michael R.; Concepcion, Javier J.; Fang, Zhen
  • Angewandte Chemie International Edition, Vol. 52, Issue 51
  • DOI: 10.1002/anie.201305951

Catalytic and Surface-Electrocatalytic Water Oxidation by Redox Mediator-Catalyst Assemblies
journal, November 2009

  • Concepcion, Javier J.; Jurss, Jonah W.; Hoertz, Paul G.
  • Angewandte Chemie International Edition, Vol. 48, Issue 50
  • DOI: 10.1002/anie.200901279

Photoinduced Electron Transfer in a Chromophore–Catalyst Assembly Anchored to TiO 2
journal, November 2012

  • Ashford, Dennis L.; Song, Wenjing; Concepcion, Javier J.
  • Journal of the American Chemical Society, Vol. 134, Issue 46
  • DOI: 10.1021/ja3084362

One Site is Enough. Catalytic Water Oxidation by [Ru(tpy)(bpm)(OH 2 )] 2+ and [Ru(tpy)(bpz)(OH 2 )] 2+
journal, December 2008

  • Concepcion, Javier J.; Jurss, Jonah W.; Templeton, Joseph L.
  • Journal of the American Chemical Society, Vol. 130, Issue 49
  • DOI: 10.1021/ja8059649

Mononuclear Ruthenium(II) Complexes That Catalyze Water Oxidation
journal, December 2008

  • Tseng, Huan-Wei; Zong, Ruifa; Muckerman, James T.
  • Inorganic Chemistry, Vol. 47, Issue 24
  • DOI: 10.1021/ic8014817

Isolated Seven-Coordinate Ru(IV) Dimer Complex with [HOHOH] Bridging Ligand as an Intermediate for Catalytic Water Oxidation
journal, August 2009

  • Duan, Lele; Fischer, Andreas; Xu, Yunhua
  • Journal of the American Chemical Society, Vol. 131, Issue 30
  • DOI: 10.1021/ja9034686

Water Oxidation with Mononuclear Ruthenium(II) Polypyridine Complexes Involving a Direct Ru IV ═O Pathway in Neutral and Alkaline Media
journal, July 2013

  • Badiei, Yosra M.; Polyansky, Dmitry E.; Muckerman, James T.
  • Inorganic Chemistry, Vol. 52, Issue 15
  • DOI: 10.1021/ic401023w

Synthesis of Phosphonic Acid Derivatized Bipyridine Ligands and Their Ruthenium Complexes
journal, October 2013

  • Norris, Michael R.; Concepcion, Javier J.; Glasson, Christopher R. K.
  • Inorganic Chemistry, Vol. 52, Issue 21
  • DOI: 10.1021/ic4014976

Highly Active and Robust Cp* Iridium Complexes for Catalytic Water Oxidation
journal, July 2009

  • Hull, Jonathan F.; Balcells, David; Blakemore, James D.
  • Journal of the American Chemical Society, Vol. 131, Issue 25
  • DOI: 10.1021/ja901270f

Proton-coupled electron transfer at modified electrodes by multiple pathways
journal, December 2011

  • Chen, Z.; Vannucci, A. K.; Concepcion, J. J.
  • Proceedings of the National Academy of Sciences, Vol. 108, Issue 52
  • DOI: 10.1073/pnas.1115769108

Water Oxidation by a Mononuclear Ruthenium Catalyst: Characterization of the Intermediates
journal, September 2011

  • Polyansky, Dmitry E.; Muckerman, James T.; Rochford, Jonathan
  • Journal of the American Chemical Society, Vol. 133, Issue 37
  • DOI: 10.1021/ja203249e

A molecular ruthenium catalyst with water-oxidation activity comparable to that of photosystem II
journal, March 2012

  • Duan, Lele; Bozoglian, Fernando; Mandal, Sukanta
  • Nature Chemistry, Vol. 4, Issue 5
  • DOI: 10.1038/nchem.1301

Application of the Rotating Ring-Disc-Electrode Technique to Water Oxidation by Surface-Bound Molecular Catalysts
journal, September 2013

  • Concepcion, Javier J.; Binstead, Robert A.; Alibabaei, Leila
  • Inorganic Chemistry, Vol. 52, Issue 19
  • DOI: 10.1021/ic402240t

Catalytic water oxidation on derivatized nanoITO
journal, January 2010

  • Chen, Zuofeng; Concepcion, Javier J.; Hull, Jonathan F.
  • Dalton Transactions, Vol. 39, Issue 30
  • DOI: 10.1039/c0dt00362j

Mechanisms of Water Oxidation from the Blue Dimer to Photosystem II
journal, March 2008

  • Liu, Feng; Concepcion, Javier J.; Jurss, Jonah W.
  • Inorganic Chemistry, Vol. 47, Issue 6
  • DOI: 10.1021/ic701249s

Artificial analogues of the oxygen-evolving complex in photosynthesis: the oxo-bridged ruthenium dimer L2(H2O)RuIII-O-RuIII(H2O)L2, L = 2,2'-bipyridyl-4,4'-dicarboxylate
journal, June 1989

  • Comte, Pascal; Nazeeruddin, Mohammad K.; Rotzinger, Francois P.
  • Journal of Molecular Catalysis, Vol. 52, Issue 1
  • DOI: 10.1016/0304-5102(89)80082-3

Mechanism of Water Oxidation Catalyzed by the μ-Oxo Dimer [(bpy) 2 (OH 2 )Ru III ORu III (OH 2 )(bpy) 2 ] 4+
journal, August 1997

  • Chronister, Chris W.; Binstead, Robert A.; Ni, Jinfeng
  • Inorganic Chemistry, Vol. 36, Issue 18
  • DOI: 10.1021/ic970393b

Catalytic and Surface-Electrocatalytic Water Oxidation by Redox Mediator-Catalyst Assemblies
journal, November 2009

  • Concepcion, Javier J.; Jurss, Jonah W.; Hoertz, Paul G.
  • Angewandte Chemie, Vol. 121, Issue 50
  • DOI: 10.1002/ange.200901279

    Works referencing / citing this record:

    CCDC 1028031: Experimental Crystal Structure Determination: VOWROQ : (2,2'-Bipyridine-6,6'-dicarboxylato)-bis(4-methylpyridine)-ruthenium perchlorate
    dataset, October 2014

    • Concepcion, Javier; Zhong, Diane; Szalda, David
    • Cambridge Structural Database (CSD)
    • DOI: 10.5517/cc13hr9n

    Catalytic and Surface-Electrocatalytic Water Oxidation by Redox Mediator-Catalyst Assemblies
    journal, November 2009

    • Concepcion, Javier J.; Jurss, Jonah W.; Hoertz, Paul G.
    • Angewandte Chemie International Edition, Vol. 48, Issue 50
    • DOI: 10.1002/anie.200901279

    Low-Overpotential Water Oxidation by a Surface-Bound Ruthenium-Chromophore-Ruthenium-Catalyst Assembly
    journal, November 2013

    • Norris, Michael R.; Concepcion, Javier J.; Fang, Zhen
    • Angewandte Chemie International Edition, Vol. 52, Issue 51
    • DOI: 10.1002/anie.201305951

    Water Oxidation by Ruthenium Complexes Incorporating Multifunctional Bipyridyl Diphosphonate Ligands
    journal, May 2016

    • Xie, Yan; Shaffer, David W.; Lewandowska-Andralojc, Anna
    • Angewandte Chemie International Edition, Vol. 55, Issue 28
    • DOI: 10.1002/anie.201601943

    Behavior of Ru-bda Water-Oxidation Catalysts in Low Oxidation States
    journal, August 2018

    • Matheu, Roc; Ghaderian, Abolfazl; Francàs, Laia
    • Chemistry - A European Journal, Vol. 24, Issue 49
    • DOI: 10.1002/chem.201801236

    Artificial analogues of the oxygen-evolving complex in photosynthesis: the oxo-bridged ruthenium dimer L2(H2O)RuIII-O-RuIII(H2O)L2, L = 2,2'-bipyridyl-4,4'-dicarboxylate
    journal, June 1989

    • Comte, Pascal; Nazeeruddin, Mohammad K.; Rotzinger, Francois P.
    • Journal of Molecular Catalysis, Vol. 52, Issue 1
    • DOI: 10.1016/0304-5102(89)80082-3

    Application of High Surface Area Tin-Doped Indium Oxide Nanoparticle Films as Transparent Conducting Electrodes
    journal, September 2010

    • Hoertz, Paul G.; Chen, Zuofeng; Kent, Caleb A.
    • Inorganic Chemistry, Vol. 49, Issue 18
    • DOI: 10.1021/ic100719r

    Water Oxidation with Mononuclear Ruthenium(II) Polypyridine Complexes Involving a Direct Ru IV ═O Pathway in Neutral and Alkaline Media
    journal, July 2013

    • Badiei, Yosra M.; Polyansky, Dmitry E.; Muckerman, James T.
    • Inorganic Chemistry, Vol. 52, Issue 15
    • DOI: 10.1021/ic401023w

    Synthesis of Phosphonic Acid Derivatized Bipyridine Ligands and Their Ruthenium Complexes
    journal, October 2013

    • Norris, Michael R.; Concepcion, Javier J.; Glasson, Christopher R. K.
    • Inorganic Chemistry, Vol. 52, Issue 21
    • DOI: 10.1021/ic4014976

    Application of the Rotating Ring-Disc-Electrode Technique to Water Oxidation by Surface-Bound Molecular Catalysts
    journal, September 2013

    • Concepcion, Javier J.; Binstead, Robert A.; Alibabaei, Leila
    • Inorganic Chemistry, Vol. 52, Issue 19
    • DOI: 10.1021/ic402240t

    Mechanisms of Water Oxidation from the Blue Dimer to Photosystem II
    journal, March 2008

    • Liu, Feng; Concepcion, Javier J.; Jurss, Jonah W.
    • Inorganic Chemistry, Vol. 47, Issue 6
    • DOI: 10.1021/ic701249s

    Mononuclear Ruthenium(II) Complexes That Catalyze Water Oxidation
    journal, December 2008

    • Tseng, Huan-Wei; Zong, Ruifa; Muckerman, James T.
    • Inorganic Chemistry, Vol. 47, Issue 24
    • DOI: 10.1021/ic8014817

    Mechanism of Water Oxidation Catalyzed by the μ-Oxo Dimer [(bpy) 2 (OH 2 )Ru III ORu III (OH 2 )(bpy) 2 ] 4+
    journal, August 1997

    • Chronister, Chris W.; Binstead, Robert A.; Ni, Jinfeng
    • Inorganic Chemistry, Vol. 36, Issue 18
    • DOI: 10.1021/ic970393b

    Catalytic oxidation of water by an oxo-bridged ruthenium dimer
    journal, July 1982

    • Gersten, Susan W.; Samuels, George J.; Meyer, Thomas J.
    • Journal of the American Chemical Society, Vol. 104, Issue 14
    • DOI: 10.1021/ja00378a053

    Water Oxidation by a Mononuclear Ruthenium Catalyst: Characterization of the Intermediates
    journal, September 2011

    • Polyansky, Dmitry E.; Muckerman, James T.; Rochford, Jonathan
    • Journal of the American Chemical Society, Vol. 133, Issue 37
    • DOI: 10.1021/ja203249e

    Photoinduced Electron Transfer in a Chromophore–Catalyst Assembly Anchored to TiO 2
    journal, November 2012

    • Ashford, Dennis L.; Song, Wenjing; Concepcion, Javier J.
    • Journal of the American Chemical Society, Vol. 134, Issue 46
    • DOI: 10.1021/ja3084362

    One Site is Enough. Catalytic Water Oxidation by [Ru(tpy)(bpm)(OH 2 )] 2+ and [Ru(tpy)(bpz)(OH 2 )] 2+
    journal, December 2008

    • Concepcion, Javier J.; Jurss, Jonah W.; Templeton, Joseph L.
    • Journal of the American Chemical Society, Vol. 130, Issue 49
    • DOI: 10.1021/ja8059649

    Highly Active and Robust Cp* Iridium Complexes for Catalytic Water Oxidation
    journal, July 2009

    • Hull, Jonathan F.; Balcells, David; Blakemore, James D.
    • Journal of the American Chemical Society, Vol. 131, Issue 25
    • DOI: 10.1021/ja901270f

    Isolated Seven-Coordinate Ru(IV) Dimer Complex with [HOHOH] Bridging Ligand as an Intermediate for Catalytic Water Oxidation
    journal, August 2009

    • Duan, Lele; Fischer, Andreas; Xu, Yunhua
    • Journal of the American Chemical Society, Vol. 131, Issue 30
    • DOI: 10.1021/ja9034686

    Mechanism of Water Oxidation by Single-Site Ruthenium Complex Catalysts
    journal, February 2010

    • Concepcion, Javier J.; Tsai, Ming-Kang; Muckerman, James T.
    • Journal of the American Chemical Society, Vol. 132, Issue 5, p. 1545-1557
    • DOI: 10.1021/ja904906v

    Single-Site, Catalytic Water Oxidation on Oxide Surfaces
    journal, November 2009

    • Chen, Zuofeng; Concepcion, Javier J.; Jurss, Jonah W.
    • Journal of the American Chemical Society, Vol. 131, Issue 43, p. 15580-15581
    • DOI: 10.1021/ja906391w

    A molecular ruthenium catalyst with water-oxidation activity comparable to that of photosystem II
    journal, March 2012

    • Duan, Lele; Bozoglian, Fernando; Mandal, Sukanta
    • Nature Chemistry, Vol. 4, Issue 5
    • DOI: 10.1038/nchem.1301

    Catalytic water oxidation on derivatized nanoITO
    journal, January 2010

    • Chen, Zuofeng; Concepcion, Javier J.; Hull, Jonathan F.
    • Dalton Transactions, Vol. 39, Issue 30
    • DOI: 10.1039/c0dt00362j

    Ruthenium water oxidation catalysts containing the non-planar tetradentate ligand, biisoquinoline dicarboxylic acid (biqaH 2 )
    journal, January 2016

    • Scherrer, Dominik; Schilling, Mauro; Luber, Sandra
    • Dalton Transactions, Vol. 45, Issue 48
    • DOI: 10.1039/c6dt03880h

    Cooperative water oxidation catalysis in a series of trinuclear metallosupramolecular ruthenium macrocycles
    journal, January 2017

    • Kunz, Valentin; Lindner, Joachim O.; Schulze, Marcus
    • Energy & Environmental Science, Vol. 10, Issue 10
    • DOI: 10.1039/c7ee01557g

    Concerted O atom-proton transfer in the O--O bond forming step in water oxidation
    journal, April 2010

    • Chen, Z.; Concepcion, J. J.; Hu, X.
    • Proceedings of the National Academy of Sciences, Vol. 107, Issue 16, p. 7225-7229
    • DOI: 10.1073/pnas.1001132107

    Proton-coupled electron transfer at modified electrodes by multiple pathways
    journal, December 2011

    • Chen, Z.; Vannucci, A. K.; Concepcion, J. J.
    • Proceedings of the National Academy of Sciences, Vol. 108, Issue 52
    • DOI: 10.1073/pnas.1115769108

    Water Oxidation by Ruthenium Complexes Incorporating Multifunctional Bipyridyl Diphosphonate Ligands
    journal, May 2016

    • Xie, Yan; Shaffer, David W.; Lewandowska-Andralojc, Anna
    • Angewandte Chemie International Edition, Vol. 55, Issue 28
    • DOI: 10.1002/anie.201601943

    Behavior of Ru-bda Water-Oxidation Catalysts in Low Oxidation States
    journal, August 2018

    • Matheu, Roc; Ghaderian, Abolfazl; Francàs, Laia
    • Chemistry - A European Journal, Vol. 24, Issue 49
    • DOI: 10.1002/chem.201801236

    Ruthenium water oxidation catalysts containing the non-planar tetradentate ligand, biisoquinoline dicarboxylic acid (biqaH 2 )
    journal, January 2016

    • Scherrer, Dominik; Schilling, Mauro; Luber, Sandra
    • Dalton Transactions, Vol. 45, Issue 48
    • DOI: 10.1039/c6dt03880h

    Cooperative water oxidation catalysis in a series of trinuclear metallosupramolecular ruthenium macrocycles
    journal, January 2017

    • Kunz, Valentin; Lindner, Joachim O.; Schulze, Marcus
    • Energy & Environmental Science, Vol. 10, Issue 10
    • DOI: 10.1039/c7ee01557g

    Impact of substituents on molecular properties and catalytic activities of trinuclear Ru macrocycles in water oxidation
    journal, January 2020

    • Meza-Chincha, Ana-Lucia; Lindner, Joachim O.; Schindler, Dorothee
    • Chemical Science
    • DOI: 10.1039/d0sc01097a

      Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.