DC Field | Value | Language |
---|---|---|
dc.contributor.author | Crandell, Douglas W. | ko |
dc.contributor.author | Xu, Song | ko |
dc.contributor.author | Smith, Jeremy M. | ko |
dc.contributor.author | Baik, Mu-Hyun | ko |
dc.date.accessioned | 2017-06-05T02:05:14Z | - |
dc.date.available | 2017-06-05T02:05:14Z | - |
dc.date.created | 2017-05-22 | - |
dc.date.created | 2017-05-22 | - |
dc.date.issued | 2017-04 | - |
dc.identifier.citation | INORGANIC CHEMISTRY, v.56, no.8, pp.4435 - 4445 | - |
dc.identifier.issn | 0020-1669 | - |
dc.identifier.uri | http://hdl.handle.net/10203/223843 | - |
dc.description.abstract | The mechanism of water oxidation performed by a recently discovered manganese pyridinophane catalyst [Mn((Py2NBu2)-Bu-t)(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 Mnill 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. | - |
dc.language | English | - |
dc.publisher | AMER CHEMICAL SOC | - |
dc.subject | OXYGEN-EVOLVING COMPLEX | - |
dc.subject | EFFECTIVE CORE POTENTIALS | - |
dc.subject | SOLVATION FREE-ENERGIES | - |
dc.subject | DENSITY-FUNCTIONAL THEORY | - |
dc.subject | TRANSITION-METAL DIMERS | - |
dc.subject | SET MODEL CHEMISTRY | - |
dc.subject | PHOTOSYSTEM-II | - |
dc.subject | MOLECULAR CALCULATIONS | - |
dc.subject | ELECTRONIC-STRUCTURE | - |
dc.subject | CRYSTAL-STRUCTURE | - |
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.identifier.wosid | 000399625600023 | - |
dc.identifier.scopusid | 2-s2.0-85018463405 | - |
dc.type.rims | ART | - |
dc.citation.volume | 56 | - |
dc.citation.issue | 8 | - |
dc.citation.beginningpage | 4435 | - |
dc.citation.endingpage | 4445 | - |
dc.citation.publicationname | INORGANIC CHEMISTRY | - |
dc.identifier.doi | 10.1021/acs.inorgchem.6b03144 | - |
dc.contributor.localauthor | Baik, Mu-Hyun | - |
dc.contributor.nonIdAuthor | Crandell, Douglas W. | - |
dc.contributor.nonIdAuthor | Xu, Song | - |
dc.contributor.nonIdAuthor | Smith, Jeremy M. | - |
dc.description.isOpenAccess | N | - |
dc.type.journalArticle | Article | - |
dc.subject.keywordPlus | OXYGEN-EVOLVING COMPLEX | - |
dc.subject.keywordPlus | EFFECTIVE CORE POTENTIALS | - |
dc.subject.keywordPlus | SOLVATION FREE-ENERGIES | - |
dc.subject.keywordPlus | DENSITY-FUNCTIONAL THEORY | - |
dc.subject.keywordPlus | TRANSITION-METAL DIMERS | - |
dc.subject.keywordPlus | SET MODEL CHEMISTRY | - |
dc.subject.keywordPlus | PHOTOSYSTEM-II | - |
dc.subject.keywordPlus | MOLECULAR CALCULATIONS | - |
dc.subject.keywordPlus | ELECTRONIC-STRUCTURE | - |
dc.subject.keywordPlus | CRYSTAL-STRUCTURE | - |
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