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Download Hi-Res ImageDownload to MS-PowerPointCite This:Inorg. Chem. 2019, 58, 6, 3676-3682
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Mechanistic Insight into Dioxygen Evolution from Diastereomeric μ-Peroxo Dinuclear Co(III) Complexes Based on Stoichiometric Electron-Transfer Oxidation

Cite this: Inorg. Chem. 2019, 58, 6, 3676–3682
Publication Date (Web):February 27, 2019
https://doi.org/10.1021/acs.inorgchem.8b03245
Copyright © 2019 American Chemical Society
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Abstract

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Stoichiometric electron-transfer (ET) oxidation of two diastereomeric μ-peroxo-μ-hydroxo dinuclear Co(III) complexes with tris(2-pyridylmethyl)amine (TPA) was examined to scrutinize the reaction mechanism of O2 evolution from the peroxo complexes, as seen in the final step in water oxidation by a Co(III)–TPA complex. The two isomeric Co(III)-peroxo complexes were synthesized and selectively isolated by recrystallization under different conditions. Although cyclic voltammograms of the two isomers in aqueous solutions showed one reversible wave at 1.1 V vs NHE at pH 2.0, two oxidation waves were observed at 1.0 and 1.4 V at pH 7.0 in the aqueous solutions, the latter of which is responsible for the O2-releasing process. At pH 7, one diastereomer showed higher reactivity than the other in O2 evolution, indicating the importance of structures of the μ-peroxo complexes in the reaction. In order to clarify the O2-evolving mechanism, we performed electron paramagnetic resonance (EPR) and resonance Raman (RR) measurements for characterizing one-electron oxidized species: The observed EPR and RR signals supported the formation of μ-superoxo-μ-hydroxo dinuclear Co(III) complexes; however, no characteristic difference was observed between two isomers in the EPR parameters including g values and superhyperfine coupling constants. ET-oxidation rate constants of the isomers were determined to be much faster than the O2-evolving rate constants, indicating that the O2-releasing step is the rate-determining step in the O2 evolution through the stoichiometric ET oxidation of the dinuclear Co(III)−μ-peroxo complexes. Therefore, the difference of reactivity in the O2 evolution for the two isomers should be derived from the thermodynamic stability of two-electron oxidized species of the dinuclear Co(III)-μ-peroxo complexes, μ-dioxygen-μ-hydroxo dinuclear Co(III) intermediates.

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The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.inorgchem.8b03245.

  • Schematic descriptions of structures of 2 and 3 (Figure S1), 1H NMR spectra of 2 and 3 (Figure S2), selected bond lengths of 3 (Figure S3), An ORTEP drawing of 3 (Figure S4), CV and SWV measurements of 2 and 3 (Figure S5), and 1H NMR spectra of 2 and 3 after oxidation reactions (Figure S6), ESI-TOF MS spectra (Figure S7), and kinetic measurements of 2e-oxidation processes (Figure S8) (PDF)

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Cited By

This article is cited by 7 publications.

  1. Yan Li, Suhashini Handunneththige, Erik R. Farquhar, Yisong Guo, Marat R. Talipov, Feifei Li, Dong Wang. Highly Reactive CoIII,IV2(μ-O)2 Diamond Core Complex That Cleaves C–H Bonds. Journal of the American Chemical Society 2019, 141 (51) , 20127-20136. https://doi.org/10.1021/jacs.9b09531
  2. Yoshihiro Shimoyama, Takahiko Kojima. Metal–Oxyl Species and Their Possible Roles in Chemical Oxidations. Inorganic Chemistry 2019, 58 (15) , 9517-9542. https://doi.org/10.1021/acs.inorgchem.8b03459
  3. J. Li, C. A. Triana, W. Wan, D. P. Adiyeri Saseendran, Y. Zhao, S. E. Balaghi, S. Heidari, G. R. Patzke. Molecular and heterogeneous water oxidation catalysts: recent progress and joint perspectives. Chemical Society Reviews 2021, 45 https://doi.org/10.1039/D0CS00978D
  4. Isabela Cristina Aguiar de Souza, Savyo de Souza Santana, Javier G. Gómez, Guilherme P. Guedes, João Madureira, Susana Maria de Ornelas Quintal, Mauricio Lanznaster. Investigation of cobalt( iii )–phenylalanine complexes for hypoxia-activated drug delivery. Dalton Transactions 2020, 49 (45) , 16425-16439. https://doi.org/10.1039/D0DT01389G
  5. Qin Xie, Qiang Fu, Hai-Bin Cui, Bo-Hong Luo, Wei-Qiang Liu, Ran Qiao, Ya-Jie Ren, Fei Chen, Hua-Xin Zhang, Jin-Qiao Long. Influence of the flexible tetrapyridines on electrocatalytic water oxidation by cobalt complexes. Polyhedron 2020, 189 , 114731. https://doi.org/10.1016/j.poly.2020.114731
  6. Biswarup Chakraborty, Ivy Ghosh, Rahul Dev Jana, Tapan Kanti Paine. Oxidative C–N bond cleavage of (2-pyridylmethyl)amine-based tetradentate supporting ligands in ternary cobalt( ii )–carboxylate complexes. Dalton Transactions 2020, 49 (11) , 3463-3472. https://doi.org/10.1039/C9DT04438H
  7. Maksym A. Dedushko, Dirk Schweitzer, Maike N. Blakely, Rodney D. Swartz, Werner Kaminsky, Julie A. Kovacs. Geometric and electronic structure of a crystallographically characterized thiolate-ligated binuclear peroxo-bridged cobalt(III) complex. JBIC Journal of Biological Inorganic Chemistry 2019, 24 (6) , 919-926. https://doi.org/10.1007/s00775-019-01686-x

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