Electron-Donating para-Substituent (X) Enhances the Water Oxidation Activity of the Catalyst Ru(4'-X-terpyridine)(phenanthroline-SO3)+

Ibañez, Miguel A.; Breyer, Colton J.; Gembicky, Milan; Malikov, Zinnun F.; Musaev, Djamaladdin G.; Grotjahn, Douglas B.

doi:10.1021/acs.inorgchem.4c04124

Electron-Donating para-Substituent (X) Enhances the Water Oxidation Activity of the Catalyst Ru(4'-X-terpyridine)(phenanthroline-SO₃)⁺

Journal Article · Fri Feb 07 00:00:00 EST 2025 · Inorganic Chemistry

DOI:https://doi.org/10.1021/acs.inorgchem.4c04124· OSTI ID:2512432

Ibañez, Miguel A. ^[1]; Breyer, Colton J. ^[1]; ^[2]; Malikov, Zinnun F. ^[3]; ^[4]; ^[1]

San Diego State University, CA (United States)
University of California-San Diego, CA (United States)
Innovation Academy, Alpharetta, GA (United States)
Emory University, Atlanta, GA (United States)

Recently, our group has developed a Ru-based water oxidation catalyst (WOC) with pendant sulfonate (1, Ru(4'-X-terpyridine)(phenanthroline-SO₃)OTf (X = H, 1a) that shows high activity under both sacrificial oxidant (CAN, Ce(NH₄)₂(NO₃)₆, Ce^IV) and electrocatalytic conditions, in both acidic and neutral media. Here, we demonstrate that the functionalization of the 4'-X-terpyridine ligand with an electron-donating substituent X = OEt (1b) makes potentials of Ru^II/Ru^III redox catalysis more negative, whereas when X = NO₂ (1c) and CF₃ (1d), potentials are more positive. For 1b, full conversion of the sacrificial oxidant Ce^IV occurred in 0.4 h (7 h for 1a), with an initial rate of 2.07 μmol O₂ s^–1 and a turnover frequency of 7.6 s^–1, which is 30-fold faster than that for 1a at [cat]₀ = 20 μM. Under electrocatalytic conditions, water oxidation by 1b is three times faster than that by the parent catalyst 1a at close to the same potential. Extensive computations have identified differences in the initial PCET steps of the water oxidation by catalysts 1a, 1b, and 1d, and demonstrated the increased probability of the O₂ formation via the oxide relay pathway in the order 1b< 1a < 1d.

View Journal Article

Research Organization:: Emory University, Atlanta, GA (United States); San Diego State University, CA (United States)

Sponsoring Organization:: National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: FG02-07ER15906; SC0018310

OSTI ID:: 2512432

Alternate ID(s):: OSTI ID: 2522679
OSTI ID: 3013387

Journal Information:: Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 7 Vol. 64; ISSN 0020-1669

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (32)

An All-Inorganic, Stable, and Highly Active Tetraruthenium Homogeneous Catalyst for Water Oxidation Geletii, Yurii V.; Botar, Bogdan; Kogerler, Paul Angewandte Chemie International Edition, Vol. 47, Issue 21, p. 3896-3899 https://doi.org/10.1002/anie.200705652	journal	May 2008
Oxygen Evolution Catalyzed by a Mononuclear Ruthenium Complex Bearing Pendant SO ₃ ⁻ Groups Yoshida, Masaki; Kondo, Mio; Torii, Sena Angewandte Chemie International Edition, Vol. 54, Issue 27 https://doi.org/10.1002/anie.201503365	journal	May 2015
Self-Assembled Amphiphilic Water Oxidation Catalysts: Control of O−O Bond Formation Pathways by Different Aggregation Patterns Yang, Bing; Jiang, Xin; Guo, Qing Angewandte Chemie International Edition, Vol. 55, Issue 21 https://doi.org/10.1002/anie.201601653	journal	April 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
An Active‐Site Sulfonate Group Creates a Fast Water Oxidation Electrocatalyst That Exhibits High Activity in Acid Nash, Aaron G.; Breyer, Colton J.; Vincenzini, Brett D. Angewandte Chemie International Edition, Vol. 60, Issue 3 https://doi.org/10.1002/anie.202008896	journal	November 2020
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
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
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
Dangling Carboxylic Group That Participates in O–O Bond Formation Reaction to Promote Water Oxidation Catalyzed by a Ruthenium Complex: Experimental Evidence of an Oxide Relay Pathway Kundu, Animesh; Barman, Suman K.; Mandal, Sukanta Inorganic Chemistry, Vol. 61, Issue 3 https://doi.org/10.1021/acs.inorgchem.1c03105	journal	January 2022
Critical Hammett Electron-Donating Ability of Substituent Groups for Efficient Water Oxidation Catalysis by Mononuclear Ruthenium Aquo Complexes Watabe, Shunsuke; Tanahashi, Yuki; Hirahara, Masanari Inorganic Chemistry, Vol. 58, Issue 19 https://doi.org/10.1021/acs.inorgchem.9b01623	journal	September 2019
Mononuclear Ruthenium-Based Water Oxidation Catalyst Supported by Anionic, Redox-Non-Innocent Ligand: Heterometallic O–O Bond Formation via Radical Coupling Pathway Kundu, Animesh; Dey, Suman Kr; Dey, Subhasis Inorganic Chemistry, Vol. 59, Issue 2 https://doi.org/10.1021/acs.inorgchem.9b03258	journal	December 2019
Evidence for Oxidative Decay of a Ru-Bound Ligand during Catalyzed Water Oxidation Kagalwala, Husain N.; Tong, Lianpeng; Zong, Ruifa ACS Catalysis, Vol. 7, Issue 4 https://doi.org/10.1021/acscatal.6b03278	journal	March 2017
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
Insights into Ru-Based Molecular Water Oxidation Catalysts: Electronic and Noncovalent-Interaction Effects on Their Catalytic Activities Duan, Lele; Wang, Lei; Inge, A. Ken Inorganic Chemistry, Vol. 52, Issue 14 https://doi.org/10.1021/ic302687d	journal	June 2013
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 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
Polyoxometalate Embedding of a Tetraruthenium(IV)-oxo-core by Template-Directed Metalation of [γ-SiW₁₀O₃₆]⁸⁻: A Totally Inorganic Oxygen-Evolving Catalyst Sartorel, Andrea; Carraro, Mauro; Scorrano, Gianfranco Journal of the American Chemical Society, Vol. 130, Issue 15, p. 5006-5007 https://doi.org/10.1021/ja077837f	journal	April 2008
New Powerful and Oxidatively Rugged Dinuclear Ru Water Oxidation Catalyst: Control of Mechanistic Pathways by Tailored Ligand Design Neudeck, Sven; Maji, Somnath; López, Isidoro Journal of the American Chemical Society, Vol. 136, Issue 1 https://doi.org/10.1021/ja409974b	journal	December 2013
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
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
Ru-bda: Unique Molecular Water-Oxidation Catalysts with Distortion Induced Open Site and Negatively Charged Ligands Zhang, Biaobiao; Sun, Licheng Journal of the American Chemical Society, Vol. 141, Issue 14 https://doi.org/10.1021/jacs.8b12862	journal	March 2019
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
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
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
The impact of secondary coordination sphere engineering on water oxidation reactivity catalysed by molecular ruthenium complexes: a next-generation approach to develop advanced catalysts Ghosh, Ayyan; Dasgupta, Sreeja; Kundu, Animesh Dalton Transactions, Vol. 51, Issue 27 https://doi.org/10.1039/D2DT01124G	journal	January 2022
Highly active and tunable catalysts for O2 evolution from water based on mononuclear ruthenium(ii) monoaquo complexes Yagi, Masayuki; Tajima, Syouhei; Komi, Manabu Dalton Transactions, Vol. 40, Issue 15 https://doi.org/10.1039/c0dt01826k	journal	January 2011
Mediator-assisted water oxidation by the ruthenium "blue dimer" cis,cis-[(bpy)2(H2O)RuORu(OH2)(bpy)2]4+ Concepcion, J. J.; Jurss, J. W.; Templeton, J. L. Proceedings of the National Academy of Sciences, Vol. 105, Issue 46 https://doi.org/10.1073/pnas.0807153105	journal	November 2008
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
Efficient water oxidation catalyzed by homogeneous cationic cobalt porphyrins with critical roles for the buffer base Wang, D.; Groves, J. T. Proceedings of the National Academy of Sciences, Vol. 110, Issue 39 https://doi.org/10.1073/pnas.1315383110	journal	September 2013
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
A Fast Soluble Carbon-Free Molecular Water Oxidation Catalyst Based on Abundant Metals Yin, Q.; Tan, J. M.; Besson, C. Science, Vol. 328, Issue 5976, p. 342-345 https://doi.org/10.1126/science.1185372	journal	March 2010

Similar Records

Improving and Measuring Water Oxidation Catalyst Viability

Technical Report · Tue Feb 03 19:00:00 EST 2026 · OSTI ID:3015964

Related Subjects

14 SOLAR ENERGY
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Catalysts
Ligands
Mathematical methods
Molecules
Water Oxidation Catalyst
Water oxidation

Electron-Donating para-Substituent (X) Enhances the Water Oxidation Activity of the Catalyst Ru(4'-X-terpyridine)(phenanthroline-SO3)+

Citation Formats

References (32)

Similar Records

Related Subjects

Electron-Donating para-Substituent (X) Enhances the Water Oxidation Activity of the Catalyst Ru(4'-X-terpyridine)(phenanthroline-SO₃)⁺