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Title: Water oxidation by Ruthenium complexes incorporating multifunctional biipyridyl diphosphonate ligands

Abstract

Here, we describe herein the synthesis and characterization of ruthenium complexes with multifunctional bipyridyl diphosphonate ligands as well as initial water oxidation studies. In these complexes, the phosphonate groups provide redox-potential leveling through charge compensation and σ donation to allow facile access to high oxidation states. These complexes display unique pH-dependent electrochemistry associated with deprotonation of the phosphonic acid groups. The position of these groups allows them to shuttle protons in and out of the catalytic site and reduce activation barriers. A mechanism for water oxidation by these catalysts is proposed on the basis of experimental results and DFT calculations. The unprecedented attack of water at a neutral six-coordinate [Ru IV] center to yield an anionic seven-coordinate [Ru IV–OH] intermediate is one of the key steps of a single-site mechanism in which all species are anionic or neutral. These complexes are among the fastest single-site catalysts reported to date.

Authors:
 [1];  [1];  [2];  [3];  [1]
  1. Brookhaven National Lab. (BNL), Upton, NY (United States)
  2. Brookhaven National Lab. (BNL), Upton, NY (United States); Adam Mickiewicz Univ., Poznan (Poland)
  3. 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) (SC-22)
OSTI Identifier:
1333198
Alternate Identifier(s):
OSTI ID: 1401855
Report Number(s):
BNL-113194-2016-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 Name: Angewandte Chemie (International Edition); Journal Volume: 55; Journal Issue: 28; Journal ID: ISSN 1433-7851
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; catalysis; electrochemistry; multifunctional; phosphates; water splitting

Citation Formats

Xie, Yan, Shaffer, David W., Lewandowska-Andralojc, Anna, Szalda, David J., and Concepcion, Javier J. Water oxidation by Ruthenium complexes incorporating multifunctional biipyridyl diphosphonate ligands. United States: N. p., 2016. Web. doi:10.1002/anie.201601943.
Xie, Yan, Shaffer, David W., Lewandowska-Andralojc, Anna, Szalda, David J., & Concepcion, Javier J. Water oxidation by Ruthenium complexes incorporating multifunctional biipyridyl diphosphonate ligands. United States. doi:10.1002/anie.201601943.
Xie, Yan, Shaffer, David W., Lewandowska-Andralojc, Anna, Szalda, David J., and Concepcion, Javier J. Wed . "Water oxidation by Ruthenium complexes incorporating multifunctional biipyridyl diphosphonate ligands". United States. doi:10.1002/anie.201601943. https://www.osti.gov/servlets/purl/1333198.
@article{osti_1333198,
title = {Water oxidation by Ruthenium complexes incorporating multifunctional biipyridyl diphosphonate ligands},
author = {Xie, Yan and Shaffer, David W. and Lewandowska-Andralojc, Anna and Szalda, David J. and Concepcion, Javier J.},
abstractNote = {Here, we describe herein the synthesis and characterization of ruthenium complexes with multifunctional bipyridyl diphosphonate ligands as well as initial water oxidation studies. In these complexes, the phosphonate groups provide redox-potential leveling through charge compensation and σ donation to allow facile access to high oxidation states. These complexes display unique pH-dependent electrochemistry associated with deprotonation of the phosphonic acid groups. The position of these groups allows them to shuttle protons in and out of the catalytic site and reduce activation barriers. A mechanism for water oxidation by these catalysts is proposed on the basis of experimental results and DFT calculations. The unprecedented attack of water at a neutral six-coordinate [RuIV] center to yield an anionic seven-coordinate [RuIV–OH]– intermediate is one of the key steps of a single-site mechanism in which all species are anionic or neutral. These complexes are among the fastest single-site catalysts reported to date.},
doi = {10.1002/anie.201601943},
journal = {Angewandte Chemie (International Edition)},
number = 28,
volume = 55,
place = {United States},
year = {Wed May 11 00:00:00 EDT 2016},
month = {Wed May 11 00:00:00 EDT 2016}
}

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Cited by: 9 works
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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
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Catalytic Water Oxidation by Single-Site Ruthenium Catalysts
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Concerted O atom-proton transfer in the O--O bond forming step in water oxidation
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Mechanism of Water Oxidation by Single-Site Ruthenium Complex Catalysts
journal, February 2010

  • Concepcion, Javier J.; Tsai, Ming-Kang; Muckerman, James T.
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