Water Oxidation by Ruthenium Complexes Incorporating Multifunctional Bipyridyl Diphosphonate Ligands

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

doi:10.1002/ange.201601943

Title: Water Oxidation by Ruthenium Complexes Incorporating Multifunctional Bipyridyl Diphosphonate Ligands

Journal Article · Wed May 11 00:00:00 EDT 2016 · Angewandte Chemie

DOI:https://doi.org/10.1002/ange.201601943· OSTI ID:1400557

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

Chemistry Division Brookhaven National Laboratory Upton NY 11973-5000 USA
Chemistry Division Brookhaven National Laboratory Upton NY 11973-5000 USA, Faculty of Chemistry Adam Mickiewicz University Umultowska 89b 61614 Poznan Poland
Department of Natural Sciences Baruch College, CUNY New York NY 10010 USA

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.

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Sponsoring Organization:: USDOE

Grant/Contract Number:: SC00112704

OSTI ID:: 1400557

Journal Information:: Angewandte Chemie, Journal Name: Angewandte Chemie Vol. 128 Journal Issue: 28; ISSN 0044-8249

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

References (23)

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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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

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