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:
-
- Brookhaven National Lab. (BNL), Upton, NY (United States)
- Brookhaven National Lab. (BNL), Upton, NY (United States); Adam Mickiewicz Univ., Poznan (Poland)
- 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}
}
Web of Science
Works referenced in this record:
Biological Water Oxidation
journal, March 2013
- Cox, Nicholas; Pantazis, Dimitrios A.; Neese, Frank
- Accounts of Chemical Research, Vol. 46, Issue 7
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
Catalytic Water Oxidation by Single-Site Ruthenium Catalysts
journal, February 2010
- Concepcion, Javier J.; Jurss, Jonah W.; Norris, Michael R.
- Inorganic Chemistry, Vol. 49, Issue 4, p. 1277-1279
Electronic Modification of the [Ru II (tpy)(bpy)(OH 2 )] 2+ Scaffold: Effects on Catalytic Water Oxidation
journal, November 2010
- Wasylenko, Derek J.; Ganesamoorthy, Chelladurai; Henderson, Matthew A.
- Journal of the American Chemical Society, Vol. 132, Issue 45
Base-enhanced catalytic water oxidation by a carboxylate–bipyridine Ru(II) complex
journal, April 2015
- Song, Na; Concepcion, Javier J.; Binstead, Robert A.
- Proceedings of the National Academy of Sciences, Vol. 112, Issue 16
Evolution of O 2 in a Seven-Coordinate Ru IV Dimer Complex with a [HOHOH] − Bridge: A Computational Study
journal, March 2010
- Nyhlén, Jonas; Duan, Lele; Åkermark, Björn
- Angewandte Chemie International Edition, Vol. 49, Issue 10
Oxo-Bridge Scenario behind Single-Site Water-Oxidation Catalysts
journal, December 2014
- López, Isidoro; Maji, Somnath; Benet-Buchholz, J.
- Inorganic Chemistry, Vol. 54, Issue 2
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
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
Oxygenic Photosynthesis
book, January 2013
- Shevela, Dmitriy; Bjorn, Lars Olof
- Natural and Artificial Photosynthesis: Solar Power as an Energy Source
Mn 4 Ca Cluster in Photosynthesis: Where and How Water is Oxidized to Dioxygen
journal, March 2014
- Yano, Junko; Yachandra, Vittal
- Chemical Reviews, Vol. 114, Issue 8
Highly Efficient Binuclear Ruthenium Catalyst for Water Oxidation
journal, February 2015
- Sander, Anett C.; Maji, Somnath; Francàs, Laia
- ChemSusChem, Vol. 8, Issue 10
Apparatus and Mechanism of Photosynthetic Water Splitting as Nature's Blueprint for Efficient Solar Energy Exploitation
book, January 2013
- Renger, Gernot
- Natural and Artificial Photosynthesis: Solar Power as an Energy Source
Mechanism of water oxidation by [Ru(bda)(L) 2 ]: the return of the “blue dimer”
journal, January 2015
- Concepcion, Javier J.; Zhong, Diane K.; Szalda, David J.
- Chemical Communications, Vol. 51, Issue 19
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
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
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
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
Photosystem II: The Reaction Center of Oxygenic Photosynthesis
journal, June 2013
- Vinyard, David J.; Ananyev, Gennady M.; Charles Dismukes, G.
- Annual Review of Biochemistry, Vol. 82, Issue 1
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
Evolution of O 2 in a Seven-Coordinate Ru IV Dimer Complex with a [HOHOH] − Bridge: A Computational Study
journal, March 2010
- Nyhlén, Jonas; Duan, Lele; Åkermark, Björn
- Angewandte Chemie, Vol. 122, Issue 10
A molecular catalyst for water oxidation that binds to metal oxide surfaces
journal, March 2015
- Sheehan, Stafford W.; Thomsen, Julianne M.; Hintermair, Ulrich
- Nature Communications, Vol. 6, Issue 1
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
Concerted O atom-proton transfer in the O--O bond forming step in water oxidation
text, January 2010
- X., Hu,; J., Concepcion, J.; W., Yang,
- The University of North Carolina at Chapel Hill University Libraries
Base-enhanced catalytic water oxidation by a carboxylate–bipyridine Ru(II) complex
text, January 2015
- J., Meyer, Thomas; K., Coggins, Michael; K., Vannucci, Aaron
- The University of North Carolina at Chapel Hill University Libraries
Works referencing / citing this record:
Redox‐Active Ligand Assisted Catalytic Water Oxidation by a Ru IV =O Intermediate
journal, January 2020
- Shi, Jing; Guo, Yu‐Hua; Xie, Fei
- Angewandte Chemie, Vol. 132, Issue 10
Redox‐Active Ligand Assisted Catalytic Water Oxidation by a Ru IV =O Intermediate
journal, January 2020
- Shi, Jing; Guo, Yu‐Hua; Xie, Fei
- Angewandte Chemie International Edition, Vol. 59, Issue 10
Quantum Chemical Study of the Mechanism of Water Oxidation Catalyzed by a Heterotrinuclear Ru 2 Mn Complex
journal, February 2019
- Li, Ying‐Ying; Gimbert, Carolina; Llobet, Antoni
- ChemSusChem, Vol. 12, Issue 5
Mononuclear Ru(II) PolyPyridyl Water Oxidation Catalysts Decorated with Perfluoroalkyl C 8 H 17 -Tag Bearing Chains : Mononuclear Ru(II) PolyPyridyl Water Oxidation Catalysts Decorated with Perfluoroalkyl C
journal, October 2019
- Tatikonda, Rajendhraprasad; Cametti, Massimo; Kalenius, Elina
- European Journal of Inorganic Chemistry, Vol. 2019, Issue 41
Water Oxidation Catalyzed by Ruthenium Complexes with 4-Hydroxypyridine-2,6-dicarboxylate as a Negatively Charged Tridentate Ligand: Water Oxidation Catalyzed by Ruthenium Complexes with 4-Hydroxypyridine-2,6-dicarboxylate as a Negatively Charged Tridentate Ligand
journal, June 2020
- Yang, Yang; Yang, Jing; Li, Fei
- European Journal of Inorganic Chemistry, Vol. 2020, Issue 23
Effects of a strong π-accepting ancillary ligand on the water oxidation activity of weakly coupled binuclear ruthenium catalysts
journal, January 2019
- Matias, Tiago A.; Rein, Francisca N.; Rocha, Reginaldo C.
- Dalton Transactions, Vol. 48, Issue 9
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
- Bhattacharyya, Arunasis; Ansari, Seraj A.; Matveev, Petr I.
- Dalton Transactions, Vol. 48, Issue 43
Structural evolution of the Ru-bms complex to the real water oxidation catalyst of Ru-bda: the bite angle matters
journal, January 2020
- Yang, Jing; Liu, Bin; Duan, Lele
- Dalton Transactions, Vol. 49, Issue 14
Pentanuclear iron catalysts for water oxidation: substituents provide two routes to control onset potentials
journal, January 2019
- Praneeth, Vijayendran K. K.; Kondo, Mio; Okamura, Masaya
- Chemical Science, Vol. 10, Issue 17
Proton Acceptor near the Active Site Lowers Dramatically the O–O Bond Formation Energy Barrier in Photocatalytic Water Splitting
journal, November 2019
- Shao, Yang; de Groot, Huub J. M.; Buda, Francesco
- The Journal of Physical Chemistry Letters, Vol. 10, Issue 24