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

Title: 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)

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

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

Grant/Contract Number:: SC00112704

OSTI ID:: 1333198

Alternate ID(s):: OSTI ID: 1401855

Report Number(s):: BNL-113194-2016-JA; R&D Project: CO026; KC0304030

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

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 61 works

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Redox‐Active Ligand Assisted Catalytic Water Oxidation by a Ru ^IV =O Intermediate Shi, Jing; Guo, Yu‐Hua; Xie, Fei Angewandte Chemie International Edition, Vol. 59, Issue 10 https://doi.org/10.1002/anie.201910614	journal	January 2020
Quantum Chemical Study of the Mechanism of Water Oxidation Catalyzed by a Heterotrinuclear Ru ₂ Mn Complex Li, Ying‐Ying; Gimbert, Carolina; Llobet, Antoni ChemSusChem, Vol. 12, Issue 5 https://doi.org/10.1002/cssc.201802395	journal	February 2019
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 Tatikonda, Rajendhraprasad; Cametti, Massimo; Kalenius, Elina European Journal of Inorganic Chemistry, Vol. 2019, Issue 41 https://doi.org/10.1002/ejic.201900579	journal	October 2019
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 Yang, Yang; Yang, Jing; Li, Fei European Journal of Inorganic Chemistry, Vol. 2020, Issue 23 https://doi.org/10.1002/ejic.202000184	journal	June 2020
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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
Proton Acceptor near the Active Site Lowers Dramatically the O–O Bond Formation Energy Barrier in Photocatalytic Water Splitting Shao, Yang; de Groot, Huub J. M.; Buda, Francesco The Journal of Physical Chemistry Letters, Vol. 10, Issue 24 https://doi.org/10.1021/acs.jpclett.9b02914	journal	November 2019

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
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electrochemistry
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phosphates
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CCDC 1430167: Experimental Crystal Structure Determination: OLOKAD : hexaaqua-magnesium bis(((2,2'-bipyridine-6,6'-diyl)bis(phosphonato))-bis(4-methylpyridine)-ruthenium(iii)) tetradecahydrate Xie, Yan; Shaffer, David W.; Lewandowska-Andralojc, Anna https://doi.org/10.5517/ccdc.csd.cc1k06f6 The current record is supplemented by this dataset	dataset	October 2015
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