The DOI matches its Crossref record; 42 of the 42 references it cites were found in a registry or an index.
Intramolecular Proton Transfer Boosts Water Oxidation Catalyzed by a Ru Complex
Open accessAbstract
We introduce a new family of complexes with the general formula [Ru(n)(tda)(py)2](m+) (n = 2, m = 0, 1; n = 3, m = 1, 2(+); n = 4, m = 2, 3(2+)), with tda(2-) being [2,2':6',2″-terpyridine]-6,6″-dicarboxylate, including complex [Ru(IV)(OH)(tda-κ-N(3)O)(py)2](+), 4H(+), which we find to be an impressive water oxidation catalyst, formed by hydroxo coordination to 3(2+) under basic conditions. The complexes are synthesized, isolated, and thoroughly characterized by analytical, spectroscopic (UV-vis, nuclear magnetic resonance, electron paramagnetic resonance), computational, and electrochemical techniques (cyclic voltammetry, differential pulse voltammetry, coulometry), including solid-state monocrystal X-ray diffraction analysis. In oxidation state IV, the Ru center is seven-coordinated and diamagnetic, whereas in oxidation state II, the complex has an unbonded dangling carboxylate and is six-coordinated while still diamagnetic. With oxidation state III, the coordination number is halfway between the coordination of oxidation states II and IV. Species generated in situ have also been characterized by spectroscopic, computational, and electrochemical techniques, together with the related species derived from a different degree of protonation and oxidation states. 4H(+) can be generated potentiometrically, or voltammetrically, from 3(2+), and both coexist in solution. While complex 3(2+) is not catalytically active, the catalytic performance of complex 4H(+) is characterized by the foot of the wave analysis, giving an impressive turnover frequency record of 8000 s(-1) at pH 7.0 and 50 000 s(-1) at pH 10.0. Density functional theory calculations provide a complete description of the water oxidation catalytic cycle of 4H(+), manifesting the key functional role of the dangling carboxylate in lowering the activation free energies that lead to O-O bond formation.
Overview
The claims and statistics of this paper haven’t been checked yet.
Run the check — free, no account needed. It reads the open-access text and checks the sources it cites.
Integrity signals
Registry
Cites
Statistics
Verification
Claims the paper makes
The claims and statistics of this paper haven’t been checked yet.
Run the check — free, no account needed. It reads the open-access text and checks the sources it cites.
Self-check
Percentages, sums and reported differences re-computed from the paper’s own numbers.
The self-check needs the paper’s full text.
Citations
Cites
Pearson, R. G. (1963) · Journal of the American Chemical Society · doi:10.1021/ja00905a001 · Cited by 10,475
Ab initio molecular orbital theory
Hehre, W. J. (1976) · Accounts of Chemical Research · doi:10.1021/ar50107a003 · Cited by 7,930
Benchmarking Heterogeneous Electrocatalysts for the Oxygen Evolution Reaction
McCrory, C. C. L., Jung, S., Peters, J. C., & Jaramillo, T. F. (2013) · Journal of the American Chemical Society · doi:10.1021/ja407115p · Cited by 7,026
Zhao, Y., & Truhlar, D. G. (2006) · The Journal of Chemical Physics · doi:10.1063/1.2370993 · Cited by 5,154
McCrory, C. C. L., Jung, S., Ferrer, I. M., Chatman, S. M., Peters, J. C., & Jaramillo, T. F. (2015) · Journal of the American Chemical Society · doi:10.1021/ja510442p · Cited by 4,145
A hole-conductor–free, fully printable mesoscopic perovskite solar cell with high stability
Mei, A., Li, X., Liu, L., Ku, Z., Liu, T., Rong, Y., Xu, M., Hu, M., Chen, J., Yang, Y., et al. (2014) · Science · doi:10.1126/science.1254763 · Cited by 3,043
Essentials of Computational Chemistry: Theories and Models
Cramer, C. J. (2002) · Cited by 2,411
Wireless Solar Water Splitting Using Silicon-Based Semiconductors and Earth-Abundant Catalysts
Reece, S. Y., Hamel, J. A., Sung, K., Jarvi, T. D., Esswein, A. J., Pijpers, J. J. H., & Nocera, D. G. (2011) · Science · doi:10.1126/science.1209816 · Cited by 1,687
Solution-Cast Metal Oxide Thin Film Electrocatalysts for Oxygen Evolution
Trotochaud, L., Ranney, J. K., Williams, K. N., & Boettcher, S. W. (2012) · Journal of the American Chemical Society · doi:10.1021/ja307507a · Cited by 1,548
Photochemical Route for Accessing Amorphous Metal Oxide Materials for Water Oxidation Catalysis
Smith, R. D. L., Prévot, M. S., Fagan, R. D., Zhang, Z., Sedach, P. A., Siu, M. K. J., Trudel, S., & Berlinguette, C. P. (2013) · Science · doi:10.1126/science.1233638 · Cited by 1,483
A molecular ruthenium catalyst with water-oxidation activity comparable to that of photosystem II
Duan, L., Bozoglian, F., Mandal, S., Stewart, B., Privalov, T., Llobet, A., & Sun, L. (2012) · Nature Chemistry · doi:10.1038/nchem.1301 · Cited by 1,257
Self-citationA Synthetic Nickel Electrocatalyst with a Turnover Frequency Above 100,000 s −1 for H 2 Production
Helm, M. L., Stewart, M. P., Bullock, R. M., DuBois, M. R., & DuBois, D. L. (2011) · Science · doi:10.1126/science.1205864 · Cited by 1,219
Catalytic oxidation of water by an oxo-bridged ruthenium dimer
Gersten, S. W., Samuels, G. J., & Meyer, T. J. (1982) · Journal of the American Chemical Society · doi:10.1021/ja00378a053 · Cited by 958
Molecular artificial photosynthesis
Berardi, S., Drouet, S., Francàs, L., Gimbert-Suriñach, C., Guttentag, M., Richmond, C., Stoll, T., & Llobet, A. (2014) · Chem. Soc. Rev. · doi:10.1039/c3cs60405e · Cited by 929
Self-citationCostentin, C., Drouet, S., Robert, M., & Savéant, J.-M. (2012) · Journal of the American Chemical Society · doi:10.1021/ja303560c · Cited by 849
One Site is Enough. Catalytic Water Oxidation by [Ru(tpy)(bpm)(OH2)]2+ and [Ru(tpy)(bpz)(OH2)]2+
Concepcion, J. J., Jurss, J. W., Templeton, J. L., & Meyer, T. J. (2008) · Journal of the American Chemical Society · doi:10.1021/ja8059649 · Cited by 674
Peverati, R., & Truhlar, D. G. (2012) · The Journal of Physical Chemistry Letters · doi:10.1021/jz201525m · Cited by 652
Evaluation of Homogeneous Electrocatalysts by Cyclic Voltammetry
Rountree, E. S., McCarthy, B. D., Eisenhart, T. T., & Dempsey, J. L. (2014) · Inorganic Chemistry · doi:10.1021/ic500658x · Cited by 589
Duan, L., Fischer, A., Xu, Y., & Sun, L. (2009) · Journal of the American Chemical Society · doi:10.1021/ja9034686 · Cited by 522
Mechanism of Water Oxidation by Single-Site Ruthenium Complex Catalysts
Concepcion, J. J., Tsai, M.-K., Muckerman, J. T., & Meyer, T. J. (2010) · Journal of the American Chemical Society · doi:10.1021/ja904906v · Cited by 482
Electrocatalytic Water Oxidation with a Copper(II) Polypeptide Complex
Zhang, M.-T., Chen, Z., Kang, P., & Meyer, T. J. (2013) · Journal of the American Chemical Society · doi:10.1021/ja3097515 · Cited by 476
Molecular Catalysts that Oxidize Water to Dioxygen
Sala, X., Romero, I., Rodríguez, M., Escriche, L., & Llobet, A. (2009) · Angewandte Chemie International Edition · doi:10.1002/anie.200802659 · Cited by 427
Self-citationConcerted O atom–proton transfer in the O—O bond forming step in water oxidation
Chen, Z., Concepcion, J. J., Hu, X., Yang, W., Hoertz, P. G., & Meyer, T. J. (2010) · Proceedings of the National Academy of Sciences · doi:10.1073/pnas.1001132107 · Cited by 338
Wasylenko, D. J., Ganesamoorthy, C., Henderson, M. A., Koivisto, B. D., Osthoff, H. D., & Berlinguette, C. P. (2010) · Journal of the American Chemical Society · doi:10.1021/ja106108y · Cited by 318
Molecular Water Oxidation Mechanisms Followed by Transition Metals: State of the Art
Sala, X., Maji, S., Bofill, R., García-Antón, J., Escriche, L., & Llobet, A. (2014) · Accounts of Chemical Research · doi:10.1021/ar400169p · Cited by 313
Self-citationOxygen−Oxygen Bond Formation Pathways Promoted by Ruthenium Complexes
Romain, S., Vigara, L., & Llobet, A. (2009) · Accounts of Chemical Research · doi:10.1021/ar900240w · Cited by 307
Self-citationThe Ru−Hbpp Water Oxidation Catalyst
Bozoglian, F., Romain, S., Ertem, M. Z., Todorova, T. K., Sens, C., Mola, J., Rodríguez, M., Romero, I., Benet-Buchholz, J., Fontrodona, X., et al. (2009) · Journal of the American Chemical Society · doi:10.1021/ja9036127 · Cited by 263
Self-citationWater Oxidation by a Mononuclear Ruthenium Catalyst: Characterization of the Intermediates
Polyansky, D. E., Muckerman, J. T., Rochford, J., Zong, R., Thummel, R. P., & Fujita, E. (2011) · Journal of the American Chemical Society · doi:10.1021/ja203249e · Cited by 199
Tong, L., Duan, L., Xu, Y., Privalov, T., & Sun, L. (2011) · Angewandte Chemie International Edition · doi:10.1002/anie.201005141 · Cited by 193
Hong, D., Mandal, S., Yamada, Y., Lee, Y.-M., Nam, W., Llobet, A., & Fukuzumi, S. (2013) · Inorganic Chemistry · doi:10.1021/ic401180r · Cited by 184
Self-citationBase-enhanced catalytic water oxidation by a carboxylate–bipyridine Ru(II) complex
Song, N., Concepcion, J. J., Binstead, R. A., Rudd, J. A., Vannucci, A. K., Dares, C. J., Coggins, M. K., & Meyer, T. J. (2015) · Proceedings of the National Academy of Sciences · doi:10.1073/pnas.1500245112 · Cited by 145
The cis‐[RuII(bpy)2(H2O)2]2+ Water‐Oxidation Catalyst Revisited
Sala, X., Ertem, M. Z., Vigara, L., Todorova, T. K., Chen, W., Rocha, R. C., Aquilante, F., Cramer, C. J., Gagliardi, L., & Llobet, A. (2010) · Angewandte Chemie International Edition · doi:10.1002/anie.201002398 · Cited by 111
Self-citationRole of ligands in catalytic water oxidation by mononuclear ruthenium complexes
Zeng, Q., Lewis, F. W., Harwood, L. M., & Hartl, F. (2015) · Coordination Chemistry Reviews · doi:10.1016/j.ccr.2015.03.003 · Cited by 90
Molecular Water Oxidation Catalysis
Llobet, A. (2014) · Wiley eBooks · doi:10.1002/9781118698648 · Cited by 87
Self-citationA Self‐Improved Water‐Oxidation Catalyst: Is One Site Really Enough?
López, I., Ertem, M. Z., Maji, S., Benet‐Buchholz, J., Keidel, A., Kuhlmann, U., Hildebrandt, P., Cramer, C. J., Batista, V. S., & Llobet, A. (2013) · Angewandte Chemie International Edition · doi:10.1002/anie.201307509 · Cited by 86
Self-citationWater Oxidation by Mononuclear Ruthenium Complexes with TPA-Based Ligands
Radaram, B., Ivie, J. A., Singh, W. M., Grudzien, R. M., Reibenspies, J. H., Webster, C. E., & Zhao, X. (2011) · Inorganic Chemistry · doi:10.1021/ic200050g · Cited by 85
Chen, G., Chen, L., Ng, S., & Lau, T. (2013) · ChemSusChem · doi:10.1002/cssc.201300561 · Cited by 76
Hirahara, M., Ertem, M. Z., Komi, M., Yamazaki, H., Cramer, C. J., & Yagi, M. (2013) · Inorganic Chemistry · doi:10.1021/ic400054k · Cited by 76
Self-citationSens, C., Rodríguez, M., Romero, I., Llobet, A., Parella, T., Sullivan, B., & Benet‐Buchholz, J. (2003) · Inorganic Chemistry · doi:10.1021/ic026114o · Cited by 71
Self-citationPrivalov, T., Åkermark, B., & Sun, L. (2011) · Chemistry - A European Journal · doi:10.1002/chem.201100901 · Cited by 43
Angeles-Boza, A. M., Ertem, M. Z., Sarma, R. J., Ibañez, C. H., Maji, S., Llobet, A., Cramer, C. J., & Roth, J. P. (2014) · Chemical Science · doi:10.1039/c3sc51919h · Cited by 39
Self-citationSubstitution Reactions in Dinuclear Ru-Hbpp Complexes: an Evaluation of Through-Space Interactions
Planas, N., Christian, G. J., Roeser, S., Mas-Marzá, E., Kollipara, M.-R., Benet‐Buchholz, J., Maseras, F., & Llobet, A. (2012) · Inorganic Chemistry · doi:10.1021/ic202225g · Cited by 23
Self-citation
Cited by
Chatenet, M., Pollet, B. G., Dekel, D. R., Dionigi, F., Deseure, J., Millet, P., Braatz, R. D., Bazant, M. Z., Eikerling, M., Staffell, I., et al. (2022) · Chemical Society Reviews · doi:10.1039/d0cs01079k · Cited by 2,025
Artificial photosynthesis: opportunities and challenges of molecular catalysts
Zhang, B., & Sun, L. (2019) · Chemical Society Reviews · doi:10.1039/c8cs00897c · Cited by 954
Quantum Algorithms for Quantum Chemistry and Quantum Materials Science
Bauer, B., Bravyi, S., Motta, M., & Chan, G. K.-L. (2020) · Chemical Reviews · doi:10.1021/acs.chemrev.9b00829 · Cited by 848
Dye-sensitized solar cells strike back
Muñoz-García, A. B., Benesperi, I., Boschloo, G., Concepcion, J. J., Delcamp, J. H., Gibson, E. A., Meyer, G. J., Pavone, M., Pettersson, H., Hagfeldt, A., et al. (2021) · Chemical Society Reviews · doi:10.1039/d0cs01336f · Cited by 544
Water Oxidation Catalysts for Artificial Photosynthesis
Ye, S., Ding, C., Liu, M., Wang, A., Huang, Q., & Li, C. (2019) · Advanced Materials · doi:10.1002/adma.201902069 · Cited by 317
Metadata
- Authors
- Matheu, R., Ertem, M. Z., Benet-Buchholz, J., Coronado, E., Batista, V. S., Sala, X., & Llobet, A.
- Venue
- Journal of the American Chemical Society
- Publisher
- American Chemical Society (ACS)
- Published
- 2015-08-12
- Volume
- 137
- Issue
- 33
- Pages
- 10786-10795
- ISSN
- 0002-7863 (ISSN-L)
- 1520-5126
- OpenAlex
- W2239220623
- Cited by
- 308
- References
- 42
- FWCI
- 11.18
- Type
- journal article
- Language
- en
- Open access
- green
About these checks
Registry, retraction, Cites and statistics results are computed, not judged, with one exception: a printed reference that no index lists is read once by a model before it counts as a citation error. Claims are extracted by a model and kept only when their quote appears verbatim in the text; each cited source is then checked, with a model’s help, for whether it says what the claim relies on. Those verdicts can be wrong — read the claim’s quote and the cited source before relying on one.
Statistics and arithmetic are recomputed, not judged.
Confidence bands are shown only for fields calibrated on our annotated test set. None is calibrated yet, so no band is shown.
What counts as a claim ›How we measure confidence ›How we check this ›
Are you an author, or do you see a problem with this page? Request a review
Data sources
Bibliographic data: Semantic Scholar, OpenAlex, Crossref.
Contains information from the Semantic Scholar Academic Graph Datasets, made available under the ODC Attribution License (ODC-BY 1.0).
Semantic Scholar’s data is described in: Kinney, R., et al. (2023). The Semantic Scholar Open Data Platform. arXiv:2301.10140.
