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DC Field | Value | Language |
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dc.citation.endPage | 3670 | - |
dc.citation.number | 7 | - |
dc.citation.startPage | 3665 | - |
dc.citation.title | PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA | - |
dc.citation.volume | 100 | - |
dc.contributor.author | Lim, Mi Hee | - |
dc.contributor.author | Rohde, Jan-Uwe | - |
dc.contributor.author | Stubna, A | - |
dc.contributor.author | Bukowski, MR | - |
dc.contributor.author | Costas, M | - |
dc.contributor.author | Ho, RYN | - |
dc.contributor.author | Munck, E | - |
dc.contributor.author | Nam, W | - |
dc.contributor.author | Que, L | - |
dc.date.accessioned | 2023-12-22T11:12:52Z | - |
dc.date.available | 2023-12-22T11:12:52Z | - |
dc.date.created | 2014-11-11 | - |
dc.date.issued | 2003-04 | - |
dc.description.abstract | The reaction of [FeII(tris(2-pyridylmethyl)amine, TPA)(NCCH3)2]2+ with 1 equiv. peracetic acid in CH3CN at -40°C results in the nearly quantitative formation of a pale green intermediate with γmax at 724 nm (ε ≈ 300 M-1·cm-1) formulated as [FeIV(O)(TPA)]2+ by a combination of spectroscopic techniques. Its electrospray mass spectrum shows a prominent feature at m/z 461, corresponding to the [FeIV(O)(TPA)(ClO4)]+ ion. The Mossbauer spectra recorded in zero field reveal a doublet with ΔEQ = 0.92(2) mm/s and δ = 0.01(2) mm/s; analysis of spectra obtained in strong magnetic fields yields parameters characteristic of S = 1 FeIV=O complexes. The presence of an FeIV=O unit is also indicated in its Fe K-edge x-ray absorption spectrum by an intense 1-s → 3-d transition and the requirement for an O/N scatterer at 1.67 A to fit the extended x-ray absorption fine structure region. The [FeIV(O)(TPA)]2+intermediate is stable at -40°C for several days but decays quantitatively on warming to [Fe2(μ-O)(μ-OAc)(TPA)2]3+. Addition of thioanisole or cyclooctene at -40°C results in the formation of thioanisole oxide (100% yield) or cyclooctene oxide (30% yield), respectively; thus [FeIV(O)(TPA)]2+ is an effective oxygen-atom transfer agent. It is proposed that the FeIV=O species derives from O-O bond heterolysis of an unobserved FeII(TPA)-acyl peroxide complex. The characterization of [FeIV(O)(TPA)]2+ as having a reactive terminal FeIV=O unit in a nonheme ligand environment lends credence to the proposed participation of analogous species in the oxygen activation mechanisms of many mononuclear nonheme iron enzymes. | - |
dc.identifier.bibliographicCitation | PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA, v.100, no.7, pp.3665 - 3670 | - |
dc.identifier.doi | 10.1073/pnas.0636830100 | - |
dc.identifier.issn | 0027-8424 | - |
dc.identifier.scopusid | 2-s2.0-0012900781 | - |
dc.identifier.uri | https://scholarworks.unist.ac.kr/handle/201301/8597 | - |
dc.identifier.url | http://www.scopus.com/inward/record.url?partnerID=HzOxMe3b&scp=0012900781 | - |
dc.identifier.wosid | 000182058400027 | - |
dc.language | 영어 | - |
dc.publisher | NATL ACAD SCIENCES | - |
dc.title | An Fe-IV = O complex of a tetradentate tripodal nonheme ligand | - |
dc.type | Article | - |
dc.description.journalRegisteredClass | scopus | - |
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