Full metadata record
DC Field | Value | Language |
---|---|---|
dc.contributor.author | 남원우 | * |
dc.date.accessioned | 2017-01-05T02:01:23Z | - |
dc.date.available | 2017-01-05T02:01:23Z | - |
dc.date.issued | 2003 | * |
dc.identifier.issn | 0027-8424 | * |
dc.identifier.other | OAK-1424 | * |
dc.identifier.uri | https://dspace.ewha.ac.kr/handle/2015.oak/233737 | - |
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 Mössbauer 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 Å 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.language | English | * |
dc.title | An FeIV=O complex of a tetradentate tripodal nonheme ligand | * |
dc.type | Article | * |
dc.relation.issue | 7 | * |
dc.relation.volume | 100 | * |
dc.relation.index | SCI | * |
dc.relation.index | SCIE | * |
dc.relation.index | SCOPUS | * |
dc.relation.startpage | 3665 | * |
dc.relation.lastpage | 3670 | * |
dc.relation.journaltitle | Proceedings of the National Academy of Sciences of the United States of America | * |
dc.identifier.doi | 10.1073/pnas.0636830100 | * |
dc.identifier.wosid | WOS:000182058400027 | * |
dc.identifier.scopusid | 2-s2.0-0012900781 | * |
dc.author.google | Hee Lim M. | * |
dc.author.google | Rohde J.-U. | * |
dc.author.google | Stubna A. | * |
dc.author.google | Bukowski M.R. | * |
dc.author.google | Costas M. | * |
dc.author.google | Ho R.Y.N. | * |
dc.author.google | Munck E. | * |
dc.author.google | Nam W. | * |
dc.author.google | Que Jr. L. | * |
dc.contributor.scopusid | 남원우(7006569723) | * |
dc.date.modifydate | 20240116111857 | * |