Linked Life Data

12644707

Source:http://linkedlifedata.com/resource/pubmed/id/12644707

Statements in which the resource exists as a subject.
PredicateObject
rdf:type
lifeskim:mentions
pubmed:issue
7
pubmed:dateCreated
2003-4-2
pubmed:abstractText
The reaction of [Fe(II)(tris(2-pyridylmethyl)amine, TPA)(NCCH(3))(2)](2+) with 1 equiv. peracetic acid in CH(3)CN at -40 degrees C results in the nearly quantitative formation of a pale green intermediate with lambda(max) at 724 nm ( epsilon approximately 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 mz 461, corresponding to the [Fe(IV)(O)(TPA)(ClO(4))](+) ion. The Mössbauer spectra recorded in zero field reveal a doublet with DeltaE(Q) = 0.92(2) mms and delta = 0.01(2) mms; 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 ON scatterer at 1.67 A to fit the extended x-ray absorption fine structure region. The [Fe(IV)(O)(TPA)](2+) intermediate is stable at -40 degrees C for several days but decays quantitatively on warming to [Fe(2)(mu-O)(mu-OAc)(TPA)(2)](3+). Addition of thioanisole or cyclooctene at -40 degrees C results in the formation of thioanisole oxide (100% yield) or cyclooctene 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 OO 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.
pubmed:grant
pubmed:commentsCorrections
http://linkedlifedata.com/resource/pubmed/commentcorrection/12644707-10698731, http://linkedlifedata.com/resource/pubmed/commentcorrection/12644707-10819623, http://linkedlifedata.com/resource/pubmed/commentcorrection/12644707-11151391, http://linkedlifedata.com/resource/pubmed/commentcorrection/12644707-11187471, http://linkedlifedata.com/resource/pubmed/commentcorrection/12644707-11749564, http://linkedlifedata.com/resource/pubmed/commentcorrection/12644707-11902894, http://linkedlifedata.com/resource/pubmed/commentcorrection/12644707-11942838, http://linkedlifedata.com/resource/pubmed/commentcorrection/12644707-12444779, http://linkedlifedata.com/resource/pubmed/commentcorrection/12644707-12586936, http://linkedlifedata.com/resource/pubmed/commentcorrection/12644707-6099143, http://linkedlifedata.com/resource/pubmed/commentcorrection/12644707-8408008, http://linkedlifedata.com/resource/pubmed/commentcorrection/12644707-8999792
pubmed:language
eng
pubmed:journal
pubmed:citationSubset
IM
pubmed:chemical
pubmed:status
MEDLINE
pubmed:month
Apr
pubmed:issn
0027-8424
pubmed:author
pubmed:issnType
Print
pubmed:day
1
pubmed:volume
100
pubmed:owner
NLM
pubmed:authorsComplete
Y
pubmed:pagination
3665-70
pubmed:dateRevised
2010-9-14
pubmed:meshHeading
pubmed:year
2003
pubmed:articleTitle
An FeIV=O complex of a tetradentate tripodal nonheme ligand.
pubmed:affiliation
Department of Chemistry and Center for Metals in Biocatalysis, University of Minnesota, 207 Pleasant Street SE, Minneapolis, MN 55455, USA.
pubmed:publicationType
Journal Article, Research Support, U.S. Gov't, P.H.S., Research Support, U.S. Gov't, Non-P.H.S., Research Support, Non-U.S. Gov't