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Article: Water oxidation catalysed by iron complex of N,N′-dimethyl-2,11-diaza[3,3](2,6)pyridinophane. Spectroscopy of iron-oxo intermediates and density functional theory calculations
Title | Water oxidation catalysed by iron complex of N,N′-dimethyl-2,11-diaza[3,3](2,6)pyridinophane. Spectroscopy of iron-oxo intermediates and density functional theory calculations |
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Authors | |
Issue Date | 2015 |
Citation | Chemical Science, 2015, v. 6, n. 10, p. 5891-5903 How to Cite? |
Abstract | © The Royal Society of Chemistry 2015. The macrocyclic [FeIII(L1)Cl2]+(1, L1 = N,N′-dimethyl-2,11-diaza[3,3](2,6)pyridinophane) complex is an active catalyst for the oxidation of water to oxygen using [NH4]2[CeIV(NO3)6] (CAN), NaIO4, or Oxone as the oxidant. The mechanism of 1-catalysed water oxidation was examined by spectroscopic methods and by18O-labelling experiments, revealing that FeIVO and/or FeVO species are likely to be involved in the reaction. The redox behaviour of 1 and these high-valent FeO species of L1 has been examined by both cyclic voltammetry and density functional theory (DFT) calculations. In aqueous solutions, the cyclic voltammograms of 1 at different pH show a pH-dependent reversible couple (E1/2= +0.46 V vs. SCE at pH 1) and an irreversible anodic wave (Epa= +1.18 V vs. SCE at pH 1) assigned to the FeIII/FeIIcouple and the FeIIIto FeIVoxidation, respectively. DFT calculations showed that the E value of the half reaction involving [FeV(L1)(O)(OH)]2+/[FeIV(L1)(O)(OH2)]2+is +1.42 V vs. SCE at pH 1. Using CAN as the oxidant at pH 1, the formation of an FeIVO reaction intermediate was suggested by ESI-MS and UV-vis absorption spectroscopic measurements, and the rate of oxygen evolution was linearly dependent on the concentrations of both 1 and CAN. Using NaIO4or Oxone as the oxidant at pH 1, the rate of oxygen evolution was linearly dependent on the concentration of 1, and a reactive FeVO species with formula [FeV(L1)(O)2]+generated by oxidation with NaIO4or Oxone was suggested by ESI-MS measurements. DFT calculations revealed that [FeV(L1)(O)2]+is capable of oxidizing water to oxygen with a reaction barrier of 15.7 kcal mol-1. |
Persistent Identifier | http://hdl.handle.net/10722/218704 |
ISSN | 2023 Impact Factor: 7.6 2023 SCImago Journal Rankings: 2.333 |
ISI Accession Number ID |
DC Field | Value | Language |
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dc.contributor.author | To, WP | - |
dc.contributor.author | Chow, WS | - |
dc.contributor.author | TSE, CW | - |
dc.contributor.author | Guan, X | - |
dc.contributor.author | Huang, JS | - |
dc.contributor.author | Che, CM | - |
dc.date.accessioned | 2015-09-18T06:50:58Z | - |
dc.date.available | 2015-09-18T06:50:58Z | - |
dc.date.issued | 2015 | - |
dc.identifier.citation | Chemical Science, 2015, v. 6, n. 10, p. 5891-5903 | - |
dc.identifier.issn | 2041-6520 | - |
dc.identifier.uri | http://hdl.handle.net/10722/218704 | - |
dc.description.abstract | © The Royal Society of Chemistry 2015. The macrocyclic [FeIII(L1)Cl2]+(1, L1 = N,N′-dimethyl-2,11-diaza[3,3](2,6)pyridinophane) complex is an active catalyst for the oxidation of water to oxygen using [NH4]2[CeIV(NO3)6] (CAN), NaIO4, or Oxone as the oxidant. The mechanism of 1-catalysed water oxidation was examined by spectroscopic methods and by18O-labelling experiments, revealing that FeIVO and/or FeVO species are likely to be involved in the reaction. The redox behaviour of 1 and these high-valent FeO species of L1 has been examined by both cyclic voltammetry and density functional theory (DFT) calculations. In aqueous solutions, the cyclic voltammograms of 1 at different pH show a pH-dependent reversible couple (E1/2= +0.46 V vs. SCE at pH 1) and an irreversible anodic wave (Epa= +1.18 V vs. SCE at pH 1) assigned to the FeIII/FeIIcouple and the FeIIIto FeIVoxidation, respectively. DFT calculations showed that the E value of the half reaction involving [FeV(L1)(O)(OH)]2+/[FeIV(L1)(O)(OH2)]2+is +1.42 V vs. SCE at pH 1. Using CAN as the oxidant at pH 1, the formation of an FeIVO reaction intermediate was suggested by ESI-MS and UV-vis absorption spectroscopic measurements, and the rate of oxygen evolution was linearly dependent on the concentrations of both 1 and CAN. Using NaIO4or Oxone as the oxidant at pH 1, the rate of oxygen evolution was linearly dependent on the concentration of 1, and a reactive FeVO species with formula [FeV(L1)(O)2]+generated by oxidation with NaIO4or Oxone was suggested by ESI-MS measurements. DFT calculations revealed that [FeV(L1)(O)2]+is capable of oxidizing water to oxygen with a reaction barrier of 15.7 kcal mol-1. | - |
dc.language | eng | - |
dc.relation.ispartof | Chemical Science | - |
dc.title | Water oxidation catalysed by iron complex of N,N′-dimethyl-2,11-diaza[3,3](2,6)pyridinophane. Spectroscopy of iron-oxo intermediates and density functional theory calculations | - |
dc.type | Article | - |
dc.identifier.email | To, WP: kevintwp@hku.hk | - |
dc.identifier.email | Guan, X: xgguan@hku.hk | - |
dc.identifier.email | Huang, JS: jshuang@hku.hk | - |
dc.identifier.email | Che, CM: cmche@hku.hk | - |
dc.identifier.authority | Huang, JS=rp00709 | - |
dc.identifier.authority | Che, CM=rp00670 | - |
dc.description.nature | published_or_final_version | - |
dc.identifier.doi | 10.1039/C5SC01680K | - |
dc.identifier.scopus | eid_2-s2.0-84982693880 | - |
dc.identifier.hkuros | 252957 | - |
dc.identifier.volume | 6 | - |
dc.identifier.isi | WOS:000361212000066 | - |
dc.identifier.issnl | 2041-6520 | - |