Linked Life Data

17685379

Source:http://linkedlifedata.com/resource/pubmed/id/17685379

Statements in which the resource exists as a subject.
PredicateObject
rdf:type
lifeskim:mentions
pubmed:issue
33
pubmed:dateCreated
2007-11-16
pubmed:abstractText
Mononuclear nonheme iron(III) complexes of tetradentate ligands containing two deprotonated amide moieties, [Fe(Me(2)bpb)Cl(H(2)O)] (3 a) and [Fe(bpc)Cl(H(2)O)] (4 a), were prepared by substitution reactions involving the previously synthesized iron(III) complexes [Et(3)NH][Fe(Me(2)bpb)Cl(2)] (3) and [Et(3)NH][Fe(bpc)Cl(2)] (4). Complexes 3 a and 4 a were characterized by IR and elemental analysis, and complex 3 a also by X-ray crystallography. Nonheme iron(III) complexes 3, 3 a, 4, and 4 a catalyze olefin epoxidation and alcohol oxidation on treatment with m-chloroperbenzoic acid. Pairwise comparisons of the reactivity of these complexes revealed that the nature of the axial ligand (Cl(-) versus H(2)O) influences the yield of oxidation products, whereas an electronic change in the supporting chelate ligand has little effect. Hydrocarbon oxidation by these catalysts was proposed to involve an iron(V) oxo species which is formed on heterolytic O-O bond cleavage of an iron acylperoxo intermediate (FeOOC(O)R). Evidence for this iron(V) oxo species was derived from KIE (k(H)/k(D)) values, H(2) (18)O exchange experiments, and the use of peroxyphenylacetic acid (PPAA) as the peracid. Our results suggest that an Fe(V)=O moiety can form in a system wherein the supporting chelate ligand comprises a mixture of neutral and anionic nitrogen donors. This work is relevant to the chemistry of mononuclear nonheme iron enzymes that are proposed to oxidize organic substrates via reaction pathways involving high-valent iron oxo species.
pubmed:language
eng
pubmed:journal
pubmed:citationSubset
IM
pubmed:chemical
pubmed:status
MEDLINE
pubmed:issn
0947-6539
pubmed:author
pubmed:issnType
Print
pubmed:volume
13
pubmed:owner
NLM
pubmed:authorsComplete
Y
pubmed:pagination
9393-8
pubmed:dateRevised
2009-8-4
pubmed:meshHeading
pubmed:year
2007
pubmed:articleTitle
Biomimetic hydrocarbon oxidation catalyzed by nonheme iron(III) complexes with peracids: evidence for an Fe(V)=O species.
pubmed:affiliation
Department of Fine Chemistry and Eco-Product and Materials Education Center, Seoul National University of Technology, Seoul, Korea.
pubmed:publicationType
Journal Article, Research Support, Non-U.S. Gov't