Intramolecular Oxyl Radical Coupling Promotes O-O Bond Formation in a Homogeneous Mononuclear Mn-based Water Oxidation Catalyst: A Computational Mechanistic Investigation
DC Field | Value | Language |
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dc.contributor.author | Douglas W. Crandell | - |
dc.contributor.author | Song Xu | - |
dc.contributor.author | Jeremy M. Smith | - |
dc.contributor.author | Mu-Hyun Baik | - |
dc.date.available | 2017-09-05T05:19:48Z | - |
dc.date.created | 2017-05-19 | - |
dc.date.issued | 2017-04 | - |
dc.identifier.issn | 0020-1669 | - |
dc.identifier.uri | https://pr.ibs.re.kr/handle/8788114/3726 | - |
dc.description.abstract | The mechanism of water oxidation performed by a recently discovered manganese pyridinophane catalyst [Mn(Py2NtBu2)(H2O)2]2+ is studied using density functional theory methods. A complete catalytic cycle is constructed and the catalytically active species is identified to consist of a MnV-bis(oxo) moiety that is generated from the resting state by a series of proton-coupled electron transfer reactions. Whereas the electronic ground state of this key intermediate is found to be a triplet, the most favorable pathway for O-O bond formation is found on the quintet potential energy surface and involves an intramolecular coupling of two oxyl radicals with opposite spins bound to the Mn-center that adopts an electronic structure most consistent formally with a high-spin MnIII ion. Therefore, the thermally accessible high-spin quintet state that constitutes a typical and innate property of a first-row transition metal center plays a critical role for catalysis. It enables facile electron transfer between the oxo moieties and the Mn-center and promotes O-O bond formation via a radical coupling reaction with a calculated reaction barrier of only 14.7 kcal mol-1. This mechanism of O-O coupling is unprecedented and provides a novel possible pathway to coupling two oxygen atoms bound to a single metal site. © 2017 American Chemical Society | - |
dc.description.uri | 1 | - |
dc.language | 영어 | - |
dc.publisher | AMER CHEMICAL SOC | - |
dc.title | Intramolecular Oxyl Radical Coupling Promotes O-O Bond Formation in a Homogeneous Mononuclear Mn-based Water Oxidation Catalyst: A Computational Mechanistic Investigation | - |
dc.type | Article | - |
dc.type.rims | ART | - |
dc.identifier.wosid | 000399625600023 | - |
dc.identifier.scopusid | 2-s2.0-85018463405 | - |
dc.identifier.rimsid | 59485 | ko |
dc.date.tcdate | 2018-10-01 | - |
dc.contributor.affiliatedAuthor | Mu-Hyun Baik | - |
dc.identifier.doi | 10.1021/acs.inorgchem.6b03144 | - |
dc.identifier.bibliographicCitation | INORGANIC CHEMISTRY, v.56, no.8, pp.4435 - 4445 | - |
dc.citation.title | INORGANIC CHEMISTRY | - |
dc.citation.volume | 56 | - |
dc.citation.number | 8 | - |
dc.citation.startPage | 4435 | - |
dc.citation.endPage | 4445 | - |
dc.date.scptcdate | 2018-10-01 | - |
dc.description.wostc | 6 | - |
dc.description.scptc | 7 | - |
dc.description.journalClass | 1 | - |
dc.description.journalRegisteredClass | scie | - |
dc.description.journalRegisteredClass | scopus | - |