On the mechanism of water oxidation by a bimetallic manganese catalyst: a density functional study.
Density functional theory is used to explore possible mechanisms that lead to water oxidation by a bimetallic manganese catalyst developed by McKenzie and co-workers. On the basis of our calculations we propose that the key active intermediate is a mixed valent Mn(III)(μ-O)Mn(IV)-O˙ oxyl radical spe...
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| Format: | Journal article |
| Language: | English |
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2011
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| _version_ | 1797088039039664128 |
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| author | Sameera, WM McKenzie, C McGrady, J |
| author_facet | Sameera, WM McKenzie, C McGrady, J |
| author_sort | Sameera, WM |
| collection | OXFORD |
| description | Density functional theory is used to explore possible mechanisms that lead to water oxidation by a bimetallic manganese catalyst developed by McKenzie and co-workers. On the basis of our calculations we propose that the key active intermediate is a mixed valent Mn(III)(μ-O)Mn(IV)-O˙ oxyl radical species, the oxyl centre being the site of nucleophilic attack by water. The mixed-valent species is in equilibrium with an isomeric diamond-core Mn(IV)(μ-O)(2)Mn(IV) structure, which acts as reservoir for the active species. The chemistry appears to be unique to pentadentate ligands because these shift the position of the equilibrium between the Mn(III)(μ-O)Mn(IV)-O˙ and Mn(IV)(μ-O)(2)Mn(IV) isomers, such that significant concentrations of the former are present in solution. |
| first_indexed | 2024-03-07T02:44:12Z |
| format | Journal article |
| id | oxford-uuid:ab7caad8-d2a0-4948-8c92-5e64b6118d00 |
| institution | University of Oxford |
| language | English |
| last_indexed | 2024-03-07T02:44:12Z |
| publishDate | 2011 |
| record_format | dspace |
| spelling | oxford-uuid:ab7caad8-d2a0-4948-8c92-5e64b6118d002022-03-27T03:22:08ZOn the mechanism of water oxidation by a bimetallic manganese catalyst: a density functional study.Journal articlehttp://purl.org/coar/resource_type/c_dcae04bcuuid:ab7caad8-d2a0-4948-8c92-5e64b6118d00EnglishSymplectic Elements at Oxford2011Sameera, WMMcKenzie, CMcGrady, JDensity functional theory is used to explore possible mechanisms that lead to water oxidation by a bimetallic manganese catalyst developed by McKenzie and co-workers. On the basis of our calculations we propose that the key active intermediate is a mixed valent Mn(III)(μ-O)Mn(IV)-O˙ oxyl radical species, the oxyl centre being the site of nucleophilic attack by water. The mixed-valent species is in equilibrium with an isomeric diamond-core Mn(IV)(μ-O)(2)Mn(IV) structure, which acts as reservoir for the active species. The chemistry appears to be unique to pentadentate ligands because these shift the position of the equilibrium between the Mn(III)(μ-O)Mn(IV)-O˙ and Mn(IV)(μ-O)(2)Mn(IV) isomers, such that significant concentrations of the former are present in solution. |
| spellingShingle | Sameera, WM McKenzie, C McGrady, J On the mechanism of water oxidation by a bimetallic manganese catalyst: a density functional study. |
| title | On the mechanism of water oxidation by a bimetallic manganese catalyst: a density functional study. |
| title_full | On the mechanism of water oxidation by a bimetallic manganese catalyst: a density functional study. |
| title_fullStr | On the mechanism of water oxidation by a bimetallic manganese catalyst: a density functional study. |
| title_full_unstemmed | On the mechanism of water oxidation by a bimetallic manganese catalyst: a density functional study. |
| title_short | On the mechanism of water oxidation by a bimetallic manganese catalyst: a density functional study. |
| title_sort | on the mechanism of water oxidation by a bimetallic manganese catalyst a density functional study |
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