Source:http://linkedlifedata.com/resource/pubmed/id/20704272
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| rdf:type | |
| lifeskim:mentions | |
| pubmed:issue |
35
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| pubmed:dateCreated |
2010-9-2
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| pubmed:abstractText |
High spin oxoiron(IV) complexes have been proposed to be a key intermediate in numerous nonheme metalloenzymes. The successful detection of similar complexes has been reported for only two synthetic systems. A new synthetic high spin oxoiron(IV) complex is now reported that can be prepared from a well-characterized oxoiron(III) species. This new oxoiron(IV) complex can also be prepared from a hydroxoiron(III) species via a proton-coupled electron transfer process--a first in synthetic chemistry. The oxoiron(IV) complex has been characterized with a variety of spectroscopic methods: FTIR studies showed a feature associated with the Fe-O bond at nu(Fe(16)O) = 798 cm(-1) that shifted to 765 cm(-1) in the (18)O complex; Mossbauer experiments show a signal with an delta = 0.02 mm/s and |DeltaE(Q)| = 0.43 mm/s, electronic parameters consistent with an Fe(IV) center, and optical spectra had visible bands at lambda(max) = 440 (epsilon(M) = 3100), 550 (epsilon(M) = 1900), and 808 (epsilon(M) = 280) nm. In addition, the oxoiron(IV) complex gave the first observable EPR features in the parallel-mode EPR spectrum with g-values at 8.19 and 4.06. A simulation for an S = 2 species with D = 4.0(5) cm(-1), E/D = 0.03, sigma(E/D) = 0.014, and g(z) = 2.04 generates a fit that accurately predicted the intensity, line shape, and position of the observed signals. These results showed that EPR spectroscopy can be a useful method for determining the properties of high spin oxoiron(IV) complexes. The oxoiron(IV) complex was crystallized at -35 degrees C, and its structure was determined by X-ray diffraction methods. The complex has a trigonal bipyramidal coordination geometry with the Fe-O unit positioned within a hydrogen bonding cavity. The Fe(IV)-O unit bond length is 1.680(1) A, which is the longest distance yet reported for a monomeric oxoiron(IV) complex.
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| pubmed:grant | |
| pubmed:commentsCorrections |
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| pubmed:language |
eng
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| pubmed:journal | |
| pubmed:citationSubset |
IM
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| pubmed:chemical | |
| pubmed:status |
MEDLINE
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| pubmed:month |
Sep
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| pubmed:issn |
1520-5126
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| pubmed:author | |
| pubmed:issnType |
Electronic
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| pubmed:day |
8
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| pubmed:volume |
132
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| pubmed:owner |
NLM
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| pubmed:authorsComplete |
Y
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| pubmed:pagination |
12188-90
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| pubmed:dateRevised |
2011-9-26
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| pubmed:meshHeading | |
| pubmed:year |
2010
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| pubmed:articleTitle |
Formation, structure, and EPR detection of a high spin Fe(IV)-oxo species derived from either an Fe(III)-oxo or Fe(III)-OH complex.
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| pubmed:affiliation |
Department of Chemistry, University of California-Irvine, 1102 Natural Sciences II, Irvine, California 92697-2025, USA.
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| pubmed:publicationType |
Journal Article,
Research Support, N.I.H., Extramural
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