Density functional theory study of redox pairs. 1. Dinuclear iron complexes that undergo multielectron redox reactions accompanied by a reversible structural change

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dc.contributor.authorBaik, Mu-Hyunko
dc.contributor.authorZiegler, Tko
dc.contributor.authorSchauer, CKko
dc.date.accessioned2016-04-12T07:48:24Z-
dc.date.available2016-04-12T07:48:24Z-
dc.date.created2015-09-11-
dc.date.created2015-09-11-
dc.date.issued2000-09-
dc.identifier.citationJOURNAL OF THE AMERICAN CHEMICAL SOCIETY, v.122, no.38, pp.9143 - 9154-
dc.identifier.issn0002-7863-
dc.identifier.urihttp://hdl.handle.net/10203/203378-
dc.description.abstractThe 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.languageEnglish-
dc.publisherAMER CHEMICAL SOC-
dc.subjectELECTRON-TRANSFER REACTIONS-
dc.subjectMETAL-METAL BOND-
dc.subjectCORRECT ASYMPTOTIC-BEHAVIOR-
dc.subjectSINGLE 2-ELECTRON PROCESS-
dc.subjectTRANSITION-STATE METHOD-
dc.subjectHIGH OXIDATION-STATES-
dc.subjectGAS-PHASE IONIZATION-
dc.subjectREDUCTION POTENTIALS-
dc.subjectNEGATIVE-IONS-
dc.subjectORGANOMETALLIC ELECTROCHEMISTRY-
dc.titleDensity functional theory study of redox pairs. 1. Dinuclear iron complexes that undergo multielectron redox reactions accompanied by a reversible structural change-
dc.typeArticle-
dc.identifier.wosid000089603400012-
dc.identifier.scopusid2-s2.0-0034721429-
dc.type.rimsART-
dc.citation.volume122-
dc.citation.issue38-
dc.citation.beginningpage9143-
dc.citation.endingpage9154-
dc.citation.publicationnameJOURNAL OF THE AMERICAN CHEMICAL SOCIETY-
dc.identifier.doi10.1021/ja993522r-
dc.contributor.localauthorBaik, Mu-Hyun-
dc.contributor.nonIdAuthorZiegler, T-
dc.contributor.nonIdAuthorSchauer, CK-
dc.type.journalArticleReview-
dc.subject.keywordPlusELECTRON-TRANSFER REACTIONS-
dc.subject.keywordPlusMETAL-METAL BOND-
dc.subject.keywordPlusCORRECT ASYMPTOTIC-BEHAVIOR-
dc.subject.keywordPlusSINGLE 2-ELECTRON PROCESS-
dc.subject.keywordPlusTRANSITION-STATE METHOD-
dc.subject.keywordPlusHIGH OXIDATION-STATES-
dc.subject.keywordPlusGAS-PHASE IONIZATION-
dc.subject.keywordPlusREDUCTION POTENTIALS-
dc.subject.keywordPlusNEGATIVE-IONS-
dc.subject.keywordPlusORGANOMETALLIC ELECTROCHEMISTRY-
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