DC Field | Value | Language |
---|---|---|
dc.contributor.author | Baik, Mu-Hyun | ko |
dc.contributor.author | Ziegler, T | ko |
dc.contributor.author | Schauer, CK | ko |
dc.date.accessioned | 2016-04-12T07:48:24Z | - |
dc.date.available | 2016-04-12T07:48:24Z | - |
dc.date.created | 2015-09-11 | - |
dc.date.created | 2015-09-11 | - |
dc.date.issued | 2000-09 | - |
dc.identifier.citation | JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, v.122, no.38, pp.9143 - 9154 | - |
dc.identifier.issn | 0002-7863 | - |
dc.identifier.uri | http://hdl.handle.net/10203/203378 | - |
dc.description.abstract | The single-two-electron reduction for the Fe-Fe bonded dinuclear complexes Fe-2(CO)(6)(mu(2)-PR2)(2) (R = CH3, 1-CH3; R = CF3, 1-CF3) is studied by electronic structure calculations based on density functional theory (DFT) methods. Several theoretical models are evaluated, including gas-phase models and models that include solvation (COSMO model) and/or countercations. The experimentally observed cleavage: of the Fe-Fe bond upon addition of electrons is reproduced in all calculations. The different theoretical models are evaluated by calculating the energy of the disproportionation reaction 2A(-) --> A + A(2-) using the energies of the complexes [1-R](0), [1-R](-), and [1-R](2-). As expected, gas-phase calculations poorly-model the experimental redox behavior, and the inclusion of salvation or: countercations is necessary to correctly: predict that the disproportionation reaction is energetically downhill. The distribution of the added electrons over the molecules and the charge distribution as a function of alkali:metal countercation (Li+, Na+, K+) are evaluated using the Hirshfeld charge analysis scheme. A qualitative correlation is found between the HOMO/LUMO energies Of the redox species and the calculated redox potentials. | - |
dc.language | English | - |
dc.publisher | AMER CHEMICAL SOC | - |
dc.subject | ELECTRON-TRANSFER REACTIONS | - |
dc.subject | METAL-METAL BOND | - |
dc.subject | CORRECT ASYMPTOTIC-BEHAVIOR | - |
dc.subject | SINGLE 2-ELECTRON PROCESS | - |
dc.subject | TRANSITION-STATE METHOD | - |
dc.subject | HIGH OXIDATION-STATES | - |
dc.subject | GAS-PHASE IONIZATION | - |
dc.subject | REDUCTION POTENTIALS | - |
dc.subject | NEGATIVE-IONS | - |
dc.subject | ORGANOMETALLIC ELECTROCHEMISTRY | - |
dc.title | Density functional theory study of redox pairs. 1. Dinuclear iron complexes that undergo multielectron redox reactions accompanied by a reversible structural change | - |
dc.type | Article | - |
dc.identifier.wosid | 000089603400012 | - |
dc.identifier.scopusid | 2-s2.0-0034721429 | - |
dc.type.rims | ART | - |
dc.citation.volume | 122 | - |
dc.citation.issue | 38 | - |
dc.citation.beginningpage | 9143 | - |
dc.citation.endingpage | 9154 | - |
dc.citation.publicationname | JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | - |
dc.identifier.doi | 10.1021/ja993522r | - |
dc.contributor.localauthor | Baik, Mu-Hyun | - |
dc.contributor.nonIdAuthor | Ziegler, T | - |
dc.contributor.nonIdAuthor | Schauer, CK | - |
dc.type.journalArticle | Review | - |
dc.subject.keywordPlus | ELECTRON-TRANSFER REACTIONS | - |
dc.subject.keywordPlus | METAL-METAL BOND | - |
dc.subject.keywordPlus | CORRECT ASYMPTOTIC-BEHAVIOR | - |
dc.subject.keywordPlus | SINGLE 2-ELECTRON PROCESS | - |
dc.subject.keywordPlus | TRANSITION-STATE METHOD | - |
dc.subject.keywordPlus | HIGH OXIDATION-STATES | - |
dc.subject.keywordPlus | GAS-PHASE IONIZATION | - |
dc.subject.keywordPlus | REDUCTION POTENTIALS | - |
dc.subject.keywordPlus | NEGATIVE-IONS | - |
dc.subject.keywordPlus | ORGANOMETALLIC ELECTROCHEMISTRY | - |
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