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dc.contributor.authorCastro, Ludovic
dc.contributor.authorBuehl, Michael
dc.date.accessioned2014-11-20T00:01:29Z
dc.date.available2014-11-20T00:01:29Z
dc.date.issued2014-01
dc.identifier.citationCastro , L & Buehl , M 2014 , ' Calculations of One-Electron Redox Potentials of Oxoiron(IV) Porphyrin Complexes ' Journal of Chemical Theory and Computation , vol. 10 , no. 1 , pp. 243-251 . DOI: 10.1021/ct400975wen
dc.identifier.issn1549-9618
dc.identifier.otherPURE: 105533633
dc.identifier.otherPURE UUID: a4f5838d-e6e5-492c-b85d-76981428756c
dc.identifier.otherWOS: 000330142400023
dc.identifier.otherScopus: 84892600578
dc.identifier.urihttp://hdl.handle.net/10023/5803
dc.description.abstractDensity functional theory calculations have been performed to calculate the one-electron redox potential for a series of oxoiron(IV) porphyrin complexes of the form [(TMP)Fe-IV(O)(L)] (TMP = 5,10,15,20-tetramesitylporphyrinate). Different axial ligands were chosen (L = none, Im, ClO4-, CH3CO2-, Cl-, F-, SCH3-) in order to compare the results with recent electrochemical experiments. The redox potentials were calculated with a Born-Haber cycle and the use of an internal reference, i.e. the absolute redox potential of ferrocene. Diverse methodologies were tested and show that the computed redox potentials depend strongly on the functional, the basis set, and the continuum models used to compute the solvation energies. Globally, BP86 gives better results for the geometries of the complexes than B3LYP and M06-L as well as more consistent values for the redox potentials. Although the results fit the experimental data for L = Im and L = ClO4-, the addition of the other anionic axial ligands to the oxoiron(IV) porphyrin complex strongly lowers the redox potential, which is in disagreement with experimental observations. This important discrepancy is discussed.en
dc.format.extent9en
dc.language.isoeng
dc.relation.ispartofJournal of Chemical Theory and Computationen
dc.rightsCopyright 2014, American Chemical Society. This document is the unedited author's version of a Submitted Work that was subsequently accepted for publication in the Journal of Chemical Theory and Computation after peer review. To access the final edited and published work, see http://pubs.acs.org/doi/abs/10.1021/ct400975wen
dc.subjectSolvation free energiesen
dc.subjectCation radical complexesen
dc.subjectContinuum dielectric theoryen
dc.subjectTransition metal complexesen
dc.subjectDensity functional theoryen
dc.subjectAxial liganden
dc.subjectCYTOCHROME-P450 ENZYMESen
dc.subjectCompound Ien
dc.subjectHorseradish peroxidaseen
dc.subjectComputational electrochemistryen
dc.titleCalculations of One-Electron Redox Potentials of Oxoiron(IV) Porphyrin Complexesen
dc.typeJournal articleen
dc.description.versionPostprinten
dc.contributor.institutionUniversity of St Andrews. School of Chemistryen
dc.contributor.institutionUniversity of St Andrews. EaSTCHEMen
dc.identifier.doihttps://doi.org/10.1021/ct400975w
dc.description.statusPeer revieweden
dc.date.embargoedUntil20-11-20


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