XAS and EPR in Situ Observation of Ru(V) Oxo Intermediate in a Ru Water Oxidation Complex**

Levin, Natalia; Casadevall, Carla; Cutsail III, George E.; Lloret‐Fillol, Julio; DeBeer, Serena; Rüdiger, Olaf

doi:10.1002/celc.202101271

Title: XAS and EPR in Situ Observation of Ru(V) Oxo Intermediate in a Ru Water Oxidation Complex**

Journal Article · Mon Dec 27 00:00:00 EST 2021 · ChemElectroChem

DOI:https://doi.org/10.1002/celc.202101271· OSTI ID:1903969

Levin, Natalia ^[1]; Casadevall, Carla ^[2]; Cutsail III, George E. ^[3]; Lloret‐Fillol, Julio ^[2]; DeBeer, Serena ^[1];

^[1]

Max Planck Institute for Chemical Energy Conversion, Mülheim an der Ruhr (Germany)
Institute of Chemical Research of Catalonia (ICIQ), Tarragona (Spain)
Max Planck Institute for Chemical Energy Conversion, Mülheim an der Ruhr (Germany); University of Duisburg-Essen (Germany)

In this study, we combine in situ spectroelectrochemistry coupled with electron paramagnetic resonance (EPR) and X-ray absorption spectroscopies (XAS) to investigate a molecular Rubased water oxidation catalyst bearing a polypyridinic backbone [Ru^II(OH₂)(Py₂Metacn)]²⁺. Although high valent key intermediate species arising in catalytic cycles of this family of compounds have remain elusive due to the lack of additional anionic ligands that could potentially stabilize them, mechanistic studies performed on this system proposed a water nucleophilic attack (WNA) mechanism for the O O bond formation. Employing in situ experimental conditions and complementary spectroscopic techniques allowed to observe intermediates that provide support for a WNA mechanism, including for the first time a Ru(V) oxo intermediate based on the Py₂Metacn ligand, in agreement with the previously proposed mechanism

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Research Organization:: SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL); Max Planck Institute for Chemical Energy Conversion, Mülheim an der Ruhr (Germany)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); Max-Planck-Society; ICIQ Foundation; European Research Foundation

Grant/Contract Number:: AC02-76SF00515; FPU14/02550

OSTI ID:: 1903969

Journal Information:: ChemElectroChem, Vol. 9, Issue 3; ISSN 2196-0216

Publisher:: ChemPubSoc EuropeCopyright Statement

Country of Publication:: United States

Language:: English

References (28)

Spectroscopic, Electrochemical and Computational Characterisation of Ru Species Involved in Catalytic Water Oxidation: Evidence for a [Ru ^V (O)(Py ₂ ^Me tacn)] Intermediate Casadevall, Carla; Codolà, Zoel; Costas, Miquel Chemistry - A European Journal, Vol. 22, Issue 29 https://doi.org/10.1002/chem.201600584	journal	June 2016
Isolation of a Ru(iv) side-on peroxo intermediate in the water oxidation reaction Casadevall, Carla; Martin-Diaconescu, Vlad; Browne, Wesley R. Nature Chemistry, Vol. 13, Issue 8 https://doi.org/10.1038/s41557-021-00702-5	journal	May 2021
A continuous in-situ EPR electrochemical reactor as a rapid in-depth mechanistic screening tool for electrocatalysis Neukermans, Sander; Hereijgers, Jonas; Vincent Ching, H. Y. Electrochemistry Communications, Vol. 97 https://doi.org/10.1016/j.elecom.2018.10.010	journal	December 2018
Water Oxidation Catalyst cis- [Ru(bpy)(5,5′-dcbpy)(H ₂ O) ₂ ] ²⁺ and Its Stabilization in Metal–Organic Framework Ezhov, Roman; Karbakhsh Ravari, Alireza; Page, Allison ACS Catalysis, Vol. 10, Issue 9 https://doi.org/10.1021/acscatal.0c00488	journal	April 2020
An Overview of Significant Achievements in Ruthenium-Based Molecular Water Oxidation Catalysis Kamdar, Jayneil; Grotjahn, Douglas Molecules, Vol. 24, Issue 3 https://doi.org/10.3390/molecules24030494	journal	January 2019
Artificial Photosynthesis: Molecular Systems for Catalytic Water Oxidation Kärkäs, Markus D.; Verho, Oscar; Johnston, Eric V. Chemical Reviews, Vol. 114, Issue 24 https://doi.org/10.1021/cr400572f	journal	October 2014
Rearranging from 6- to 7-coordination initiates the catalytic activity: An EPR study on a Ru-bda water oxidation catalyst Daniel, Quentin; Huang, Ping; Fan, Ting Coordination Chemistry Reviews, Vol. 346 https://doi.org/10.1016/j.ccr.2017.02.019	journal	September 2017
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
Experimental demonstration of radicaloid character in a RuV=O intermediate in catalytic water oxidation Moonshiram, D.; Alperovich, I.; Concepcion, J. J. Proceedings of the National Academy of Sciences, Vol. 110, Issue 10 https://doi.org/10.1073/pnas.1222102110	journal	February 2013
Characterization of Intermediary Redox States of the Water Oxidation Catalyst, [Ru(bpy) ₂ (OH ₂ )] ₂ O ⁴⁺ Cape, Jonathan L.; Lymar, Sergei V.; Lightbody, Travis Inorganic Chemistry, Vol. 48, Issue 10 https://doi.org/10.1021/ic9001219	journal	May 2009
Making Oxygen with Ruthenium Complexes Concepcion, Javier J.; Jurss, Jonah W.; Brennaman, M. Kyle Accounts of Chemical Research, Vol. 42, Issue 12 https://doi.org/10.1021/ar9001526	journal	December 2009
Surface-Promoted Evolution of Ru-bda Coordination Oligomers Boosts the Efficiency of Water Oxidation Molecular Anodes Gil-Sepulcre, Marcos; Lindner, Joachim O.; Schindler, Dorothee Journal of the American Chemical Society, Vol. 143, Issue 30 https://doi.org/10.1021/jacs.1c04738	journal	July 2021
A Microfluidic Channel Flow Cell for Electrochemical ESR Wain, Andrew J.; Compton, Richard G.; Le Roux, Rudolph The Journal of Physical Chemistry B, Vol. 110, Issue 51 https://doi.org/10.1021/jp064903b	journal	November 2006
In Situ EPR Study of Chemical Reactions in Q-Band at Higher Temperatures: A Challenge for Elucidating Structure−Reactivity Relationships in Catalysis Stösser, Reinhard; Marx, Ulrich; Herrmann, Werner Journal of the American Chemical Society, Vol. 132, Issue 28 https://doi.org/10.1021/ja1035418	journal	June 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
Oxygen Evolution from Water Catalyzed by Mononuclear Ruthenium Complexes with a Triazamacrocyclic Ligand in a Facial Fashion Yoshida, Masaki; Masaoka, Shigeyuki; Sakai, Ken Chemistry Letters, Vol. 38, Issue 7 https://doi.org/10.1246/cl.2009.702	journal	July 2009
Detection of the site protected 7-coordinate RuV = O species and its chemical reactivity to enable catalytic water oxidation Pineda-Galvan, Yuliana; Ravari, Alireza K.; Shmakov, Sergei Journal of Catalysis, Vol. 375 https://doi.org/10.1016/j.jcat.2019.05.014	journal	July 2019
Spectroscopic Analysis of Catalytic Water Oxidation by [Ru ^II (bpy)(tpy)H ₂ O] ²⁺ Suggests That Ru ^V ═O Is Not a Rate-Limiting Intermediate Pushkar, Yulia; Moonshiram, Dooshaye; Purohit, Vatsal Journal of the American Chemical Society, Vol. 136, Issue 34 https://doi.org/10.1021/ja506586b	journal	August 2014
Electronic Structure of Oxidized Complexes Derived from cis -[Ru ^II (bpy) ₂ (H ₂ O) ₂ ] ²⁺ and Its Photoisomerization Mechanism Planas, Nora; Vigara, Laura; Cady, Clyde Inorganic Chemistry, Vol. 50, Issue 21 https://doi.org/10.1021/ic201686c	journal	November 2011
Unexpected ligand lability in condition of water oxidation catalysis Yan, Lifen; Zong, Ruifa; Pushkar, Yulia Journal of Catalysis, Vol. 330 https://doi.org/10.1016/j.jcat.2015.07.018	journal	October 2015
The Key Ru ^V =O Intermediate of Site-Isolated Mononuclear Water Oxidation Catalyst Detected by in Situ X-ray Absorption Spectroscopy Lebedev, Dmitry; Pineda-Galvan, Yuliana; Tokimaru, Yuki Journal of the American Chemical Society, Vol. 140, Issue 1 https://doi.org/10.1021/jacs.7b11388	journal	December 2017
Mechanistic Analysis of Water Oxidation Catalyst cis-[Ru(bpy)2(H2O)2]2+: Effect of Dimerization Erdman, Darren; Pineda-Galvan, Yuliana; Pushkar, Yulia Catalysts, Vol. 7, Issue 12 https://doi.org/10.3390/catal7020039	journal	January 2017
Studies on transition-metal oxo and nitrido complexes. 12. Synthesis, spectroscopic properties, and reactions of stable ruthenium(V) and osmium(V) oxo complexes containing .alpha.-hydroxy carboxylate and .alpha.-amino carboxylate ligands Dengel, Andrew C.; Griffith, William P. Inorganic Chemistry, Vol. 30, Issue 4 https://doi.org/10.1021/ic00004a054	journal	February 1991
Catalysis of Mononuclear Aquaruthenium Complexes in Oxygen Evolution from Water: A New Radical Coupling Path using Hydroxocerium(IV) Species Yoshida, Masaki; Masaoka, Shigeyuki; Abe, Jiro Chemistry - An Asian Journal, Vol. 5, Issue 11 https://doi.org/10.1002/asia.201000323	journal	September 2010
Structure and Electronic Configurations of the Intermediates of Water Oxidation in Blue Ruthenium Dimer Catalysis Moonshiram, Dooshaye; Jurss, Jonah W.; Concepcion, Javier J. Journal of the American Chemical Society, Vol. 134, Issue 10 https://doi.org/10.1021/ja208636f	journal	March 2012
The hydrogen economy in the 21st century: a sustainable development scenario Barreto, L.; Makihira, A.; Riahi, K. International Journal of Hydrogen Energy, Vol. 28, Issue 3 https://doi.org/10.1016/S0360-3199(02)00074-5	journal	March 2003
The design of TACN-based molecular systems for different supramolecular functions Macedi, Eleonora; Bencini, Andrea; Caltagirone, Claudia Coordination Chemistry Reviews, Vol. 407 https://doi.org/10.1016/j.ccr.2019.213151	journal	March 2020
Molecular Catalysts for Water Oxidation Blakemore, James D.; Crabtree, Robert H.; Brudvig, Gary W. Chemical Reviews, Vol. 115, Issue 23 https://doi.org/10.1021/acs.chemrev.5b00122	journal	July 2015

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
spectroelectrochemistry
water oxidation
ruthenium
catalyst
in situ electrochemistry

Title: XAS and EPR in Situ Observation of Ru(V) Oxo Intermediate in a Ru Water Oxidation Complex**

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