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

Abstract

Abstract 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)
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 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. https://doi.org/10.1002/anie.201601943
Xie, Yan, Shaffer, David W., Lewandowska-Andralojc, Anna, Szalda, David J., and Concepcion, Javier J. 2016. "Water oxidation by Ruthenium complexes incorporating multifunctional biipyridyl diphosphonate ligands". United States. https://doi.org/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 = {Abstract 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.},
doi = {10.1002/anie.201601943},
url = {https://www.osti.gov/biblio/1333198}, journal = {Angewandte Chemie (International Edition)},
issn = {1433-7851},
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: 61 works
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Works referenced in this record:

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journal, December 2014


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journal, August 2009


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A molecular ruthenium catalyst with water-oxidation activity comparable to that of photosystem II
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Evolution of O 2 in a Seven-Coordinate Ru IV Dimer Complex with a [HOHOH] Bridge: A Computational Study
journal, March 2010


A molecular catalyst for water oxidation that binds to metal oxide surfaces
journal, March 2015


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


Concerted O atom-proton transfer in the O--O bond forming step in water oxidation
text, January 2010


Base-enhanced catalytic water oxidation by a carboxylate–bipyridine Ru(II) complex
text, January 2015


Works referencing / citing this record:

Redox‐Active Ligand Assisted Catalytic Water Oxidation by a Ru IV =O Intermediate
journal, January 2020


Redox‐Active Ligand Assisted Catalytic Water Oxidation by a Ru IV =O Intermediate
journal, January 2020


Quantum Chemical Study of the Mechanism of Water Oxidation Catalyzed by a Heterotrinuclear Ru 2 Mn Complex
journal, February 2019


Effects of a strong π-accepting ancillary ligand on the water oxidation activity of weakly coupled binuclear ruthenium catalysts
journal, January 2019


Unfolding the complexation and extraction of Am 3+ and Eu 3+ using N-heterocyclic aromatic diphosphonic acids: a combined experimental and DFT study
journal, January 2019


Structural evolution of the Ru-bms complex to the real water oxidation catalyst of Ru-bda: the bite angle matters
journal, January 2020


Pentanuclear iron catalysts for water oxidation: substituents provide two routes to control onset potentials
journal, January 2019


Proton Acceptor near the Active Site Lowers Dramatically the O–O Bond Formation Energy Barrier in Photocatalytic Water Splitting
journal, November 2019