DC Field | Value | Language |
---|---|---|
dc.contributor.author | Lim, Mi Hee | ko |
dc.contributor.author | Rohde, JU | ko |
dc.contributor.author | Stubna, A | ko |
dc.contributor.author | Bukowski, MR | ko |
dc.contributor.author | Costas, M | ko |
dc.contributor.author | Ho, RYN | ko |
dc.contributor.author | Munck, E | ko |
dc.contributor.author | Nam, W | ko |
dc.contributor.author | Que, L | ko |
dc.date.accessioned | 2018-02-21T06:25:42Z | - |
dc.date.available | 2018-02-21T06:25:42Z | - |
dc.date.created | 2018-02-08 | - |
dc.date.created | 2018-02-08 | - |
dc.date.created | 2018-02-08 | - |
dc.date.issued | 2003-04 | - |
dc.identifier.citation | PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA, v.100, no.7, pp.3665 - 3670 | - |
dc.identifier.issn | 0027-8424 | - |
dc.identifier.uri | http://hdl.handle.net/10203/240341 | - |
dc.description.abstract | The reaction of [Fell(tris(2-pyridylmethyl)amine, TPA)(NCCH3)(2)](2+) with 1 equiv. peracetic acid in CH3CN at -40degreesC results in the nearly quantitative formation of a pale green intermediate with lambda(max) at 724 nm (epsilon approximate to 300 M-1-cm(-1)) formulated as [Fe-IV(O)(TPA)](2+) by a combination of spectroscopic techniques. Its electrospray mass spectrum shows a prominent feature at m/z 461, corresponding to the [Fe-IV(O)(TPA)(CIO4)](+) ion. The Mossbauer spectra recorded in zero field reveal a doublet with DeltaE(Q) = 0.92(2) mm/s and delta = 0.01(2) mm/s; analysis of spectra obtained in strong magnetic fields yields parameters characteristic of S = 1 Fe-IV==O complexes. The presence of an Fe-IV==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 Angstrom to fit the extended x-ray absorption fine structure region. The [Fe-IV(O)(TPA)](2+) intermediate is stable at -40degreesC for several days but decays quantitatively on warming to [Fe-2(mu-O)(mu-OAc)(TPA)(2)](3+). Addition of thioanisole or cycloodene at -40degreesC results in the formation of thioanisole oxide (100% yield) or cycloodene oxide (30% yield), respectively; thus [Fe-IV(O)(TPA)](2+) is an effective oxygen-atom transfer agent. It is proposed that the Fe-IV=O species derives from O-O bond heterolysis of an unobserved Fe-II(TPA)-acyl peroxide complex. The characterization of [Fe-IV(O)(TPA)](2+) as having a reactive terminal Fe-IV==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.language | English | - |
dc.publisher | NATL ACAD SCIENCES | - |
dc.title | An Fe-IV = O complex of a tetradentate tripodal nonheme ligand | - |
dc.type | Article | - |
dc.identifier.wosid | 000182058400027 | - |
dc.identifier.scopusid | 2-s2.0-0012900781 | - |
dc.type.rims | ART | - |
dc.citation.volume | 100 | - |
dc.citation.issue | 7 | - |
dc.citation.beginningpage | 3665 | - |
dc.citation.endingpage | 3670 | - |
dc.citation.publicationname | PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA | - |
dc.identifier.doi | 10.1073/pnas.0636830100 | - |
dc.contributor.localauthor | Lim, Mi Hee | - |
dc.contributor.nonIdAuthor | Rohde, JU | - |
dc.contributor.nonIdAuthor | Stubna, A | - |
dc.contributor.nonIdAuthor | Bukowski, MR | - |
dc.contributor.nonIdAuthor | Costas, M | - |
dc.contributor.nonIdAuthor | Ho, RYN | - |
dc.contributor.nonIdAuthor | Munck, E | - |
dc.contributor.nonIdAuthor | Nam, W | - |
dc.contributor.nonIdAuthor | Que, L | - |
dc.description.isOpenAccess | N | - |
dc.type.journalArticle | Article | - |
dc.subject.keywordAuthor | high-valent iron-oxo | - |
dc.subject.keywordAuthor | oxygen activation | - |
dc.subject.keywordAuthor | oxygenases | - |
dc.subject.keywordPlus | FE-2(MU-O)(2) DIAMOND CORE | - |
dc.subject.keywordPlus | WATER-SOLUBLE METALLOPORPHYRINS | - |
dc.subject.keywordPlus | MONOOXYGENASE CATALYTIC CYCLE | - |
dc.subject.keywordPlus | IRON(III) PORPHYRIN COMPLEX | - |
dc.subject.keywordPlus | RAY-ABSORPTION-SPECTROSCOPY | - |
dc.subject.keywordPlus | REDUCTASE INTERMEDIATE-X | - |
dc.subject.keywordPlus | OXO-HYDROXO TAUTOMERISM | - |
dc.subject.keywordPlus | DISTINCT IRON SITES | - |
dc.subject.keywordPlus | METHANE MONOOXYGENASE | - |
dc.subject.keywordPlus | RIBONUCLEOTIDE REDUCTASE | - |
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