Quantum-Chemical Study of the Four-Electron Catalytic Oxidation of Water to Dioxygen in the Presence of Dinuclear and Tetranuclear Hydroxide Complexes of Cobalt(III) and Iron(III): Intermediates of the Catalytic Cycle and Their Relative Energies Full article
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Journal of Molecular Catalysis (Continued after 1994 as Journal of Molecular Catalysis A: Chemical and Journal of Molecular Catalysis B: Enzymatic)
ISSN: 0304-5102 |
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| Output data | Year: 1994, Volume: 91, Number: 1, Pages: 71-82 Pages count : 12 DOI: 10.1016/0304-5102(94)00014-X | ||
| Tags | Cobalt, Hydroxo complexes, Iron, Oxidation, Quantum-chemical calculations, Water | ||
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Abstract:
Quantum-chemical calculations have been performed to elucidate possible intermediates and their relative energies in the closed cycle of the catalytic oxidation of water to dioxygen by one-electron oxidants. Di- and tetranuclear hydroxocomplexes of CoIII and FeIII served as the simplest prototypes of artificial catalysts for the reaction under study. The predicted intermediates of the consecutive one-electron oxidation of the reaction site accompanied by its deprotonation appear to be analogs of well-known chemical structures of the type of transition metal complexes with dioxygen ligands. It is found that during the process only one metal ion undergoes the redox transformations, changing its valence state from IV to II, while the second metal ion serves mainly to stabilize the intermediates resulting from the oxidized water molecule. Thus, it confirms the well-known hypothesis at least on the dinuclear nature of the “oxygen evolving reaction centre”. Release of a dioxygen molecule most probably occurs after the third oxidation of the initial form of the reaction site. The calculated energies of intermediates participating in the catalytic cycle are in reasonable agreement with available experimental data.
Cite:
Filatov M.J.
, Elizarova G.L.
, Gerasimov O.V.
, Zhidomirov G.M.
, Parmon V.N.
Quantum-Chemical Study of the Four-Electron Catalytic Oxidation of Water to Dioxygen in the Presence of Dinuclear and Tetranuclear Hydroxide Complexes of Cobalt(III) and Iron(III): Intermediates of the Catalytic Cycle and Their Relative Energies
Journal of Molecular Catalysis (Continued after 1994 as Journal of Molecular Catalysis A: Chemical and Journal of Molecular Catalysis B: Enzymatic). 1994. V.91. N1. P.71-82. DOI: 10.1016/0304-5102(94)00014-X WOS Scopus РИНЦ ANCAN OpenAlex
Quantum-Chemical Study of the Four-Electron Catalytic Oxidation of Water to Dioxygen in the Presence of Dinuclear and Tetranuclear Hydroxide Complexes of Cobalt(III) and Iron(III): Intermediates of the Catalytic Cycle and Their Relative Energies
Journal of Molecular Catalysis (Continued after 1994 as Journal of Molecular Catalysis A: Chemical and Journal of Molecular Catalysis B: Enzymatic). 1994. V.91. N1. P.71-82. DOI: 10.1016/0304-5102(94)00014-X WOS Scopus РИНЦ ANCAN OpenAlex
Dates:
| Submitted: | Jul 12, 1993 |
| Accepted: | Jan 11, 1994 |
| Published print: | Jun 27, 1994 |
| Published online: | Oct 2, 2001 |
Identifiers:
| Web of science: | WOS:A1994NW34500007 |
| Scopus: | 2-s2.0-0028446172 |
| Elibrary: | 31079117 |
| Chemical Abstracts: | 1994:466685 |
| Chemical Abstracts (print): | 121:66685 |
| OpenAlex: | W1974394331 |