Water oxidation by Ruthenium complexes incorporating multifunctional biipyridyl diphosphonate ligands

Xie, Yan; Shaffer, David W.; Lewandowska-Andralojc, Anna; Szalda, David J.; Concepcion, Javier J.

doi:10.1002/anie.201601943

Water oxidation by Ruthenium complexes incorporating multifunctional biipyridyl diphosphonate ligands

Journal Article · Wed May 11 00:00:00 EDT 2016 · Angewandte Chemie (International Edition)

DOI:https://doi.org/10.1002/anie.201601943· OSTI ID:1333198

Xie, Yan ^[1]; Shaffer, David W. ^[1]; Lewandowska-Andralojc, Anna ^[2]; Szalda, David J. ^[3]; Concepcion, Javier J. ^[1]

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)

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.

View Accepted Manuscript (DOE)

Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Organization:: USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

OSTI ID:: 1333198

Alternate ID(s):: OSTI ID: 1401855

Report Number(s):: BNL--113194-2016-JA; KC0304030

Journal Information:: Angewandte Chemie (International Edition), Journal Name: Angewandte Chemie (International Edition) Journal Issue: 28 Vol. 55; ISSN 1433-7851

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

References (25)

Oxygenic Photosynthesis Shevela, Dmitriy; Bjorn, Lars Olof Natural and Artificial Photosynthesis: Solar Power as an Energy Source https://doi.org/10.1002/9781118659892.ch2	book	January 2013
Apparatus and Mechanism of Photosynthetic Water Splitting as Nature's Blueprint for Efficient Solar Energy Exploitation Renger, Gernot Natural and Artificial Photosynthesis: Solar Power as an Energy Source https://doi.org/10.1002/9781118659892.ch3	book	January 2013
Evolution of O ₂ in a Seven-Coordinate Ru ^IV Dimer Complex with a [HOHOH] ⁻ Bridge: A Computational Study Nyhlén, Jonas; Duan, Lele; Åkermark, Björn Angewandte Chemie, Vol. 122, Issue 10 https://doi.org/10.1002/ange.200906439	journal	March 2010
Evolution of O ₂ in a Seven-Coordinate Ru ^IV Dimer Complex with a [HOHOH] ⁻ Bridge: A Computational Study Nyhlén, Jonas; Duan, Lele; Åkermark, Björn Angewandte Chemie International Edition, Vol. 49, Issue 10 https://doi.org/10.1002/anie.200906439	journal	March 2010
Highly Efficient Binuclear Ruthenium Catalyst for Water Oxidation Sander, Anett C.; Maji, Somnath; Francàs, Laia ChemSusChem, Vol. 8, Issue 10 https://doi.org/10.1002/cssc.201403344	journal	February 2015
Biological Water Oxidation Cox, Nicholas; Pantazis, Dimitrios A.; Neese, Frank Accounts of Chemical Research, Vol. 46, Issue 7 https://doi.org/10.1021/ar3003249	journal	March 2013
Mn ₄ Ca Cluster in Photosynthesis: Where and How Water is Oxidized to Dioxygen Yano, Junko; Yachandra, Vittal Chemical Reviews, Vol. 114, Issue 8 https://doi.org/10.1021/cr4004874	journal	March 2014
Oxo-Bridge Scenario behind Single-Site Water-Oxidation Catalysts López, Isidoro; Maji, Somnath; Benet-Buchholz, J. Inorganic Chemistry, Vol. 54, Issue 2 https://doi.org/10.1021/ic502603e	journal	December 2014
Mechanisms of Water Oxidation from the Blue Dimer to Photosystem II Liu, Feng; Concepcion, Javier J.; Jurss, Jonah W. Inorganic Chemistry, Vol. 47, Issue 6 https://doi.org/10.1021/ic701249s	journal	March 2008
Mononuclear Ruthenium(II) Complexes That Catalyze Water Oxidation Tseng, Huan-Wei; Zong, Ruifa; Muckerman, James T. Inorganic Chemistry, Vol. 47, Issue 24 https://doi.org/10.1021/ic8014817	journal	December 2008
Catalytic Water Oxidation by Single-Site Ruthenium Catalysts Concepcion, Javier J.; Jurss, Jonah W.; Norris, Michael R. Inorganic Chemistry, Vol. 49, Issue 4, p. 1277-1279 https://doi.org/10.1021/ic901437e	journal	February 2010
Catalytic oxidation of water by an oxo-bridged ruthenium dimer Gersten, Susan W.; Samuels, George J.; Meyer, Thomas J. Journal of the American Chemical Society, Vol. 104, Issue 14 https://doi.org/10.1021/ja00378a053	journal	July 1982
Electronic Modification of the [Ru ^II (tpy)(bpy)(OH ₂ )] ²⁺ Scaffold: Effects on Catalytic Water Oxidation Wasylenko, Derek J.; Ganesamoorthy, Chelladurai; Henderson, Matthew A. Journal of the American Chemical Society, Vol. 132, Issue 45 https://doi.org/10.1021/ja106108y	journal	November 2010
One Site is Enough. Catalytic Water Oxidation by [Ru(tpy)(bpm)(OH ₂ )] ²⁺ and [Ru(tpy)(bpz)(OH ₂ )] ²⁺ Concepcion, Javier J.; Jurss, Jonah W.; Templeton, Joseph L. Journal of the American Chemical Society, Vol. 130, Issue 49 https://doi.org/10.1021/ja8059649	journal	December 2008
Isolated Seven-Coordinate Ru(IV) Dimer Complex with [HOHOH] ⁻ Bridging Ligand as an Intermediate for Catalytic Water Oxidation Duan, Lele; Fischer, Andreas; Xu, Yunhua Journal of the American Chemical Society, Vol. 131, Issue 30 https://doi.org/10.1021/ja9034686	journal	August 2009
Mechanism of Water Oxidation by Single-Site Ruthenium Complex Catalysts Concepcion, Javier J.; Tsai, Ming-Kang; Muckerman, James T. Journal of the American Chemical Society, Vol. 132, Issue 5, p. 1545-1557 https://doi.org/10.1021/ja904906v	journal	February 2010
Single-Site, Catalytic Water Oxidation on Oxide Surfaces Chen, Zuofeng; Concepcion, Javier J.; Jurss, Jonah W. Journal of the American Chemical Society, Vol. 131, Issue 43, p. 15580-15581 https://doi.org/10.1021/ja906391w	journal	November 2009
A molecular ruthenium catalyst with water-oxidation activity comparable to that of photosystem II Duan, Lele; Bozoglian, Fernando; Mandal, Sukanta Nature Chemistry, Vol. 4, Issue 5 https://doi.org/10.1038/nchem.1301	journal	March 2012
A molecular catalyst for water oxidation that binds to metal oxide surfaces Sheehan, Stafford W.; Thomsen, Julianne M.; Hintermair, Ulrich Nature Communications, Vol. 6, Issue 1 https://doi.org/10.1038/ncomms7469	journal	March 2015
Mechanism of water oxidation by [Ru(bda)(L) ₂ ]: the return of the “blue dimer” Concepcion, Javier J.; Zhong, Diane K.; Szalda, David J. Chemical Communications, Vol. 51, Issue 19 https://doi.org/10.1039/C4CC07968J	journal	January 2015
Concerted O atom-proton transfer in the O--O bond forming step in water oxidation Chen, Z.; Concepcion, J. J.; Hu, X. Proceedings of the National Academy of Sciences, Vol. 107, Issue 16, p. 7225-7229 https://doi.org/10.1073/pnas.1001132107	journal	April 2010
Base-enhanced catalytic water oxidation by a carboxylate–bipyridine Ru(II) complex Song, Na; Concepcion, Javier J.; Binstead, Robert A. Proceedings of the National Academy of Sciences, Vol. 112, Issue 16 https://doi.org/10.1073/pnas.1500245112	journal	April 2015
Photosystem II: The Reaction Center of Oxygenic Photosynthesis Vinyard, David J.; Ananyev, Gennady M.; Charles Dismukes, G. Annual Review of Biochemistry, Vol. 82, Issue 1 https://doi.org/10.1146/annurev-biochem-070511-100425	journal	June 2013
Concerted O atom-proton transfer in the O--O bond forming step in water oxidation X., Hu,; J., Concepcion, J.; W., Yang, The University of North Carolina at Chapel Hill University Libraries https://doi.org/10.17615/fjb7-tv45	text	January 2010
Base-enhanced catalytic water oxidation by a carboxylate–bipyridine Ru(II) complex J., Meyer, Thomas; K., Coggins, Michael; K., Vannucci, Aaron The University of North Carolina at Chapel Hill University Libraries https://doi.org/10.17615/w0m4-tb12	text	January 2015

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O–O bond formation in ruthenium-catalyzed water oxidation: single-site nucleophilic attack vs. O–O radical coupling Shaffer, David W.; Xie, Yan; Concepcion, Javier J. Chemical Society Reviews, Vol. 46, Issue 20 https://doi.org/10.1039/c7cs00542c	journal	January 2017
Artificial photosynthesis: opportunities and challenges of molecular catalysts Zhang, Biaobiao; Sun, Licheng Chemical Society Reviews, Vol. 48, Issue 7 https://doi.org/10.1039/c8cs00897c	journal	January 2019
Effects of a strong π-accepting ancillary ligand on the water oxidation activity of weakly coupled binuclear ruthenium catalysts Matias, Tiago A.; Rein, Francisca N.; Rocha, Reginaldo C. Dalton Transactions, Vol. 48, Issue 9 https://doi.org/10.1039/c8dt04963g	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 Bhattacharyya, Arunasis; Ansari, Seraj A.; Matveev, Petr I. Dalton Transactions, Vol. 48, Issue 43 https://doi.org/10.1039/c9dt03422f	journal	January 2019
Structural evolution of the Ru-bms complex to the real water oxidation catalyst of Ru-bda: the bite angle matters Yang, Jing; Liu, Bin; Duan, Lele Dalton Transactions, Vol. 49, Issue 14 https://doi.org/10.1039/c9dt04693c	journal	January 2020
Pentanuclear iron catalysts for water oxidation: substituents provide two routes to control onset potentials Praneeth, Vijayendran K. K.; Kondo, Mio; Okamura, Masaya Chemical Science, Vol. 10, Issue 17 https://doi.org/10.1039/c9sc00678h	journal	January 2019

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