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

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:
Report Number(s):
BNL-113194-2016-JA
Journal ID: ISSN 1433-7851; R&D Project: CO026; KC0304030
Grant/Contract Number:
SC00112704
Type:
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
Research Org:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; catalysis; electrochemistry; multifunctional; phosphates; water splitting
OSTI Identifier:
1333198
Alternate Identifier(s):
OSTI ID: 1401855

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., 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.. 2016. "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 = {2016},
month = {5}
}

Works referenced in this record:

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