Second Coordination Sphere Effects in an Evolved Ru Complex Based on Highly Adaptable Ligand Results in Rapid Water Oxidation Catalysis

Vereshchuk, Nataliia; Matheu, Roc; Benet-Buchholz, Jordi; Pipelier, Muriel; Lebreton, Jacques; Dubreuil, Didier; Tessier, Arnaud; Gimbert-Suriñach, Carolina; Ertem, Mehmed Z.; Llobet, Antoni

doi:10.1021/jacs.9b11935

Second Coordination Sphere Effects in an Evolved Ru Complex Based on Highly Adaptable Ligand Results in Rapid Water Oxidation Catalysis

Journal Article · Tue Feb 11 00:00:00 EST 2020 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.9b11935· OSTI ID:1608772

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Barcelona Institute of Science and Technology (BIST), Tarragona (Spain). Inst. of Chemical Research of Catalonia (ICIQ); Rovira i Virgili University (URV), Tarragona (Spain). Dept. of Physical and Inorganic Chemistry
Barcelona Institute of Science and Technology (BIST), Tarragona (Spain). Inst. of Chemical Research of Catalonia (ICIQ)
Univ. of Nantes (France)
Brookhaven National Lab. (BNL), Upton, NY (United States)
Barcelona Institute of Science and Technology (BIST), Tarragona (Spain). Inst. of Chemical Research of Catalonia (ICIQ); Univ. Autonoma de Barcelona (Spain)

A new Ru complex containing the deprotonated 2,2':6',2"-terpyridine-6,6"-diphosphonic acid (H₄tPa) and pyridine (py) of general formula [Ru^II(H₃tPa-κ-N³O)(py)₂]⁺, 2⁺, has been prepared and thoroughly characterized by means of spectroscopic and electrochemical techniques, X-ray diffraction analysis, and density functional theory (DFT) calculations. Complex 2⁺ presents a dynamic behavior in the solution that involves the synchronous coordination and the decoordination of the dangling phosphonic groups of the tPa^4– ligand. Yet, at oxidation state IV, complex 2⁺ becomes seven coordinated with the two phosphonic groups now bonded to the metal center. Further, at this oxidation state at neutral and basic pH, the Ru complex undergoes the coordination of an exogenous OH^– group from the solvent that leads to an intramolecular aromatic O atom insertion into the CH bond of one of the pyridyl groups, forming the corresponding phenoxo-phosphonate Ru complex [Ru^III(tPaO-κ-N²O_PO_C)(py)₂]^2–, 4^2–, where tPaO^5– is the 3-(hydroxo-[2,2':6',2"-terpyridine]-6,6"-diyl)bis(phosphonate) ligand. This new in situ generated Ru complex, 4^2–, has been isolated and spectroscopically and electrochemically characterized. In addition, a crystal structure has been also obtained using single-crystal X-ray diffraction techniques. Complex 4^2– turns out to be an exceptional water oxidation catalyst achieving record maximum turnover frequencies (TOF_max) on the order of 16 000 s^–1. A mechanistic analysis complemented with DFT calculations has further been carried out, showing the critical role of intramolecular second coordination sphere effects exerted by the phosphonate groups in lowering the activation energy at the rate-determining step.

View Accepted Manuscript (DOE)

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

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

Grant/Contract Number:: SC0012704

OSTI ID:: 1608772

Report Number(s):: BNL--213794-2020-JAAM

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 11 Vol. 142; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (54)

Ruthenium Complexes of 2,2′-Bipyridine-6,6′-diphosphonate Ligands for Water Oxidation Kamdar, Jayneil M.; Marelius, David C.; Moore, Curtis E. ChemCatChem, Vol. 8, Issue 19 https://doi.org/10.1002/cctc.201600359	journal	September 2016
Supramolecular Water Oxidation with Ru-bda-Based Catalysts Richmond, Craig J.; Matheu, Roc; Poater, Albert Chemistry - A European Journal, Vol. 20, Issue 52 https://doi.org/10.1002/chem.201405144	journal	November 2014
Behavior of Ru-bda Water-Oxidation Catalysts in Low Oxidation States Matheu, Roc; Ghaderian, Abolfazl; Francàs, Laia Chemistry - A European Journal, Vol. 24, Issue 49 https://doi.org/10.1002/chem.201801236	journal	August 2018
The M06 suite of density functionals for main group thermochemistry, thermochemical kinetics, noncovalent interactions, excited states, and transition elements: two new functionals and systematic testing of four M06-class functionals and 12 other functionals Zhao, Yan; Truhlar, Donald G. Theoretical Chemistry Accounts, Vol. 120, Issue 1-3 https://doi.org/10.1007/s00214-007-0310-x	journal	July 2007
Catalysts by Design: The Power of Theory Hammes-Schiffer, Sharon Accounts of Chemical Research, Vol. 50, Issue 3 https://doi.org/10.1021/acs.accounts.6b00555	journal	March 2017
Evaluation of Homogeneous Electrocatalysts by Cyclic Voltammetry Rountree, Eric S.; McCarthy, Brian D.; Eisenhart, Thomas T. Inorganic Chemistry, Vol. 53, Issue 19 https://doi.org/10.1021/ic500658x	journal	September 2014
Mechanistic Studies of the Oxygen Evolution Reaction by a Cobalt-Phosphate Catalyst at Neutral pH Surendranath, Yogesh; Kanan, Matthew W.; Nocera, Daniel G. Journal of the American Chemical Society, Vol. 132, Issue 46 https://doi.org/10.1021/ja106102b	journal	November 2010
Intramolecular Proton Transfer Boosts Water Oxidation Catalyzed by a Ru Complex Matheu, Roc; Ertem, Mehmed Z.; Benet-Buchholz, Jordi Journal of the American Chemical Society, Vol. 137, Issue 33 https://doi.org/10.1021/jacs.5b06541	journal	August 2015
Structural and Spectroscopic Characterization of Reaction Intermediates Involved in a Dinuclear Co–Hbpp Water Oxidation Catalyst Gimbert-Suriñach, Carolina; Moonshiram, Dooshaye; Francàs, Laia Journal of the American Chemical Society, Vol. 138, Issue 47 https://doi.org/10.1021/jacs.6b08532	journal	November 2016
Water Oxidation by Ruthenium Complexes Incorporating Multifunctional Bipyridyl Diphosphonate Ligands Xie, Yan; Shaffer, David W.; Lewandowska-Andralojc, Anna Angewandte Chemie International Edition, Vol. 55, Issue 28 https://doi.org/10.1002/anie.201601943	journal	May 2016
Foot of the Wave Analysis for Mechanistic Elucidation and Benchmarking Applications in Molecular Water Oxidation Catalysis Matheu, Roc; Neudeck, Sven; Meyer, Franc ChemSusChem, Vol. 9, Issue 23 https://doi.org/10.1002/cssc.201601286	journal	November 2016
Catalytic Oxidation of Water to Dioxygen by Mononuclear Ru Complexes Bearing a 2,6‐Pyridinedicarboxylato Ligand Hoque, Md Asmaul; Benet‐Buchholz, Jordi; Llobet, Antoni ChemSusChem, Vol. 12, Issue 9 https://doi.org/10.1002/cssc.201802996	journal	November 2018
Synthesis, structure and redox properties of ruthenium complexes containing the tpm facial and the trpy meridional tridentate ligands Laurent, François; Plantalech, Elena; Donnadieu, Bruno Polyhedron, Vol. 18, Issue 25 https://doi.org/10.1016/S0277-5387(99)00270-3	journal	November 1999
Seven Coordinated Molecular Ruthenium–Water Oxidation Catalysts: A Coordination Chemistry Journey: Focus Review Matheu, Roc; Ertem, Mehmed Z.; Gimbert-Suriñach, Carolina Chemical Reviews, Vol. 119, Issue 6 https://doi.org/10.1021/acs.chemrev.8b00537	journal	January 2019
Reinvestigation of Water Oxidation Catalyzed by a Dinuclear Cobalt Polypyridine Complex: Identification of CoO _x as a Real Heterogeneous Catalyst Wang, Jia-Wei; Sahoo, Pathik; Lu, Tong-Bu ACS Catalysis, Vol. 6, Issue 8 https://doi.org/10.1021/acscatal.6b00798	journal	July 2016
Hydrogen Bonding Rescues Overpotential in Seven-Coordinated Ru Water Oxidation Catalysts Matheu, Roc; Ertem, Mehmed Z.; Gimbert-Suriñach, Carolina ACS Catalysis, Vol. 7, Issue 10 https://doi.org/10.1021/acscatal.7b01860	journal	August 2017
The Role of Seven-Coordination in Ru-Catalyzed Water Oxidation Matheu, Roc; Ertem, Mehmed Z.; Pipelier, Muriel ACS Catalysis, Vol. 8, Issue 3 https://doi.org/10.1021/acscatal.7b03638	journal	January 2018
Artificial Photosynthesis: From Nanosecond Electron Transfer to Catalytic Water Oxidation Kärkäs, Markus D.; Johnston, Eric V.; Verho, Oscar Accounts of Chemical Research, Vol. 47, Issue 1 https://doi.org/10.1021/ar400076j	journal	August 2013
Molecular Water Oxidation Mechanisms Followed by Transition Metals: State of the Art Sala, Xavier; Maji, Somnath; Bofill, Roger Accounts of Chemical Research, Vol. 47, Issue 2 https://doi.org/10.1021/ar400169p	journal	December 2013
Proton-Coupled Electron Transfer Huynh, My Hang V.; Meyer, Thomas J. Chemical Reviews, Vol. 107, Issue 11 https://doi.org/10.1021/cr0500030	journal	November 2007
Thermochemistry of Proton-Coupled Electron Transfer Reagents and its Implications Warren, Jeffrey J.; Tronic, Tristan A.; Mayer, James M. Chemical Reviews, Vol. 110, Issue 12 https://doi.org/10.1021/cr100085k	journal	December 2010
Solar Water Splitting Cells Walter, Michael G.; Warren, Emily L.; McKone, James R. Chemical Reviews, Vol. 110, Issue 11, p. 6446-6473 https://doi.org/10.1021/cr1002326	journal	November 2010
Solar Energy Supply and Storage for the Legacy and Nonlegacy Worlds Cook, Timothy R.; Dogutan, Dilek K.; Reece, Steven Y. Chemical Reviews, Vol. 110, Issue 11 https://doi.org/10.1021/cr100246c	journal	November 2010
Proton-Coupled Electron Transfer Weinberg, David R.; Gagliardi, Christopher J.; Hull, Jonathan F. Chemical Reviews, Vol. 112, Issue 7 https://doi.org/10.1021/cr200177j	journal	April 2012
Determination of pK_a Values of 4-Phosphonato-2,2‘:6‘,2‘ ‘-Terpyridine and Its Ruthenium(II)-Based Photosensitizer by NMR, Potentiometric, and Spectrophotometric Methods Nazeeruddin, Md. K.; Zakeeruddin, S. M.; Humphry-Baker, R. Inorganic Chemistry, Vol. 39, Issue 20 https://doi.org/10.1021/ic000215+	journal	September 2000
Redox and spectral properties of monooxo polypyridyl complexes of ruthenium and osmium in aqueous media Takeuchi, Kenneth J.; Thompson, Mark S.; Pipes, David W. Inorganic Chemistry, Vol. 23, Issue 13 https://doi.org/10.1021/ic00181a014	journal	June 1984
Chemical Approaches to Artificial Photosynthesis. 2 Alstrum-Acevedo, James H.; Brennaman, M. Kyle; Meyer, Thomas J. Inorganic Chemistry, Vol. 44, Issue 20 https://doi.org/10.1021/ic050904r	journal	October 2005
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
Intramolecular Ligand Hydroxylation: Mechanistic High-Pressure Studies on the Reaction of a Dinuclear Copper(I) Complex with Dioxygen Becker, Michael; Schindler, Siegfried; Karlin, Kenneth D. Inorganic Chemistry, Vol. 38, Issue 9 https://doi.org/10.1021/ic981066m	journal	May 1999
Chemically catalyzed net electrochemical oxidation of alcohols, aldehydes, and unsaturated hydrocarbons using the system (trpy)(bpy)Ru(OH2)2+/(trpy)(bpy)RuO2+ Moyer, Bruce A.; Thompson, Mark S.; Meyer, Thomas J. Journal of the American Chemical Society, Vol. 102, Issue 7 https://doi.org/10.1021/ja00527a030	journal	March 1980
Equilibrium acidities in dimethyl sulfoxide Brauman, John I.; Bryson, Juliette A.; Kahl, Dean C. Journal of the American Chemical Society, Vol. 92, Issue 22 https://doi.org/10.1021/ja00725a071	journal	November 1970
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
Turnover Numbers, Turnover Frequencies, and Overpotential in Molecular Catalysis of Electrochemical Reactions. Cyclic Voltammetry and Preparative-Scale Electrolysis Costentin, Cyrille; Drouet, Samuel; Robert, Marc Journal of the American Chemical Society, Vol. 134, Issue 27, p. 11235-11242 https://doi.org/10.1021/ja303560c	journal	June 2012
Benchmarking Hydrogen Evolving Reaction and Oxygen Evolving Reaction Electrocatalysts for Solar Water Splitting Devices McCrory, Charles C. L.; Jung, Suho; Ferrer, Ivonne M. Journal of the American Chemical Society, Vol. 137, Issue 13 https://doi.org/10.1021/ja510442p	journal	March 2015
Electrolyte-Dependent Electrosynthesis and Activity of Cobalt-Based Water Oxidation Catalysts Surendranath, Yogesh; Dincǎ, Mircea; Nocera, Daniel G. Journal of the American Chemical Society, Vol. 131, Issue 7 https://doi.org/10.1021/ja807769r	journal	February 2009
Oxygen−Oxygen Bond Formation by the Ru-Hbpp Water Oxidation Catalyst Occurs Solely via an Intramolecular Reaction Pathway Romain, Sophie; Bozoglian, Fernando; Sala, Xavier Journal of the American Chemical Society, Vol. 131, Issue 8 https://doi.org/10.1021/ja808166d	journal	March 2009
Lability and Basicity of Bipyridine-Carboxylate-Phosphonate Ligand Accelerate Single-Site Water Oxidation by Ruthenium-Based Molecular Catalysts Shaffer, David W.; Xie, Yan; Szalda, David J. Journal of the American Chemical Society, Vol. 139, Issue 43 https://doi.org/10.1021/jacs.7b06096	journal	October 2017
The Carboxylate Ligand as an Oxide Relay in Catalytic Water Oxidation Zhan, Shaoqi; De Gracia Triviño, Juan Angel; Ahlquist, Mårten S. G. Journal of the American Chemical Society, Vol. 141, Issue 26 https://doi.org/10.1021/jacs.9b02585	journal	June 2019
Proton-Coupled Electron Transfer in Solution, Proteins, and Electrochemistry ^† Hammes-Schiffer, Sharon; Soudackov, Alexander V. The Journal of Physical Chemistry B, Vol. 112, Issue 45 https://doi.org/10.1021/jp805876e	journal	November 2008
Factors Governing Metal−Ligand Distances and Coordination Geometries of Metal Complexes Kuppuraj, Gopi; Dudev, Minko; Lim, Carmay The Journal of Physical Chemistry B, Vol. 113, Issue 9 https://doi.org/10.1021/jp807972e	journal	March 2009
Universal Solvation Model Based on Solute Electron Density and on a Continuum Model of the Solvent Defined by the Bulk Dielectric Constant and Atomic Surface Tensions Marenich, Aleksandr V.; Cramer, Christopher J.; Truhlar, Donald G. The Journal of Physical Chemistry B, Vol. 113, Issue 18, p. 6378-6396 https://doi.org/10.1021/jp810292n	journal	May 2009
Direct-Coupling O ₂ Bond Forming a Pathway in Cobalt Oxide Water Oxidation Catalysts Wang, Lee-Ping; Van Voorhis, Troy The Journal of Physical Chemistry Letters, Vol. 2, Issue 17 https://doi.org/10.1021/jz201021n	journal	August 2011
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
The development of molecular water oxidation catalysts Matheu, Roc; Garrido-Barros, Pablo; Gil-Sepulcre, Marcos Nature Reviews Chemistry, Vol. 3, Issue 5 https://doi.org/10.1038/s41570-019-0096-0	journal	April 2019
Molecular artificial photosynthesis Berardi, Serena; Drouet, Samuel; Francàs, Laia Chem. Soc. Rev., Vol. 43, Issue 22 https://doi.org/10.1039/C3CS60405E	journal	January 2014
How to make an efficient and robust molecular catalyst for water oxidation Garrido-Barros, Pablo; Gimbert-Suriñach, Carolina; Matheu, Roc Chemical Society Reviews, Vol. 46, Issue 20 https://doi.org/10.1039/C7CS00248C	journal	January 2017
Mechanisms of molecular water oxidation in solution and on oxide surfaces Meyer, Thomas J.; Sheridan, Matthew V.; Sherman, Benjamin D. Chemical Society Reviews, Vol. 46, Issue 20 https://doi.org/10.1039/C7CS00465F	journal	January 2017
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
Charge-transfer-energy-dependent oxygen evolution reaction mechanisms for perovskite oxides Hong, Wesley T.; Stoerzinger, Kelsey A.; Lee, Yueh-Lin Energy & Environmental Science, Vol. 10, Issue 10 https://doi.org/10.1039/C7EE02052J	journal	January 2017
Stereoselective Synthesis of α-Amino-H-phosphinic Acids and Derivatives Ordóñez, Mario; Viveros-Ceballos, José; Sayago, Francisco Synthesis, Vol. 49, Issue 05 https://doi.org/10.1055/s-0036-1588617	journal	October 2016
A new local density functional for main-group thermochemistry, transition metal bonding, thermochemical kinetics, and noncovalent interactions Zhao, Yan; Truhlar, Donald G. The Journal of Chemical Physics, Vol. 125, Issue 19, Article No. 194101 https://doi.org/10.1063/1.2370993	journal	November 2006
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
Research opportunities to advance solar energy utilization Lewis, N. S. Science, Vol. 351, Issue 6271 https://doi.org/10.1126/science.aad1920	journal	January 2016
What would it take for renewably powered electrosynthesis to displace petrochemical processes? De Luna, Phil; Hahn, Christopher; Higgins, Drew Science, Vol. 364, Issue 6438 https://doi.org/10.1126/science.aav3506	journal	April 2019

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