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Rohde, Jan-Uwe
Transition Metal Chemistry
Research Interests
  • Inorganic chemistry, coordination chemistry, organometallic chemistry, chemical synthesis, catalysis, green chemistry, inorganic reaction mechanisms.


An Fe-IV = O complex of a tetradentate tripodal nonheme ligand

DC Field Value Language Lim, Mi Hee ko Rohde, Jan-Uwe ko Stubna, A ko Bukowski, MR ko Costas, M ko Ho, RYN ko Munck, E ko Nam, W ko Que, L ko 2014-11-12T00:41:44Z - 2014-11-11 ko 2003-04 ko
dc.identifier.citation PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA, v.100, no.7, pp.3665 - 3670 ko
dc.identifier.issn 0027-8424 ko
dc.identifier.uri -
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. ko
dc.description.statementofresponsibility close -
dc.language 영어 ko
dc.publisher NATL ACAD SCIENCES ko
dc.title An Fe-IV = O complex of a tetradentate tripodal nonheme ligand ko
dc.type ARTICLE ko
dc.identifier.scopusid 2-s2.0-0012900781 ko
dc.identifier.wosid 000182058400027 ko
dc.type.rims ART ko
dc.description.wostc 212 *
dc.description.scopustc 0 * 2015-05-06 * 2014-11-11 *
dc.identifier.doi 10.1073/pnas.0636830100 ko
dc.identifier.url ko
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