Source:http://linkedlifedata.com/resource/pubmed/id/15725005
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| Predicate | Object |
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| rdf:type | |
| lifeskim:mentions | |
| pubmed:issue |
8
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| pubmed:dateCreated |
2005-2-23
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| pubmed:abstractText |
The reaction between an Fe(III) complex and O(2) to afford a stable catalytically active diiron(IV)-mu-oxo compound is described. Phosphonium salts of orange five-coordinated Fe(III)-TAML complexes with an axial aqua ligand ([PPh(4)]1-H(2)O, tetraamidato macrocyclic Fe(III) species derived from 3,3,6,6,9,9-hexamethyl-3,4,8,9-tetrahydro-1H-1,4,8,11-benzotetraazacyclotridecine-2,5,7,10(6H,11H)-tetraone) react rapidly with O(2) in CH(2)Cl(2) or other weakly coordinating solvents to produce black mu-oxo-bridged diiron(IV) complexes, 2, in high yields. Complexes 2 have been characterized by X-ray crystallography (2 cases), microanalytical data, mass spectrometry, UV/Vis, Mossbauer, and (1)H NMR spectroscopies. Mossbauer data show that the diamagnetic Fe-O-Fe unit contains antiferromagnetically coupled S = 1 Fe(IV) sites; diamagnetic (1)H NMR spectra are observed. The oxidation of PPh(3) to OPPh(3) by 2 was confirmed by UV/Vis and GC-MS. Labeling experiments with (18)O(2) and H(2)(18)O established that the bridging oxygen atom of 2 derives from O(2). Complexes 2 catalyze the selective oxidation of benzylic alcohols into the corresponding aldehydes and bleach rapidly organic dyes, such as Orange II in MeCN-H(2)O mixtures; reactivity evidence suggests that free radical autoxidation is not involved. This work highlights a promising development for the advancement of green oxidation technology, as O(2) is an abundant, clean, and inexpensive oxidizing agent.
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| pubmed:language |
eng
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| pubmed:journal | |
| pubmed:status |
PubMed-not-MEDLINE
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| pubmed:month |
Mar
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| pubmed:issn |
0002-7863
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| pubmed:author |
pubmed-author:BeachEvan SES,
pubmed-author:CollinsTerrence JTJ,
pubmed-author:GhoshAnindyaA,
pubmed-author:HorwitzColin PCP,
pubmed-author:KinoshitaIsamuI,
pubmed-author:MünckEckardE,
pubmed-author:NishiokaTakanoriT,
pubmed-author:RyabovAlexander DAD,
pubmed-author:Tiago de OliveiraFilipeF,
pubmed-author:YanoToshihiroT
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| pubmed:issnType |
Print
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| pubmed:day |
2
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| pubmed:volume |
127
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| pubmed:owner |
NLM
|
| pubmed:authorsComplete |
Y
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| pubmed:pagination |
2505-13
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| pubmed:year |
2005
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| pubmed:articleTitle |
Catalytically active mu-Oxodiiron(IV) oxidants from Iron(III) and dioxygen.
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| pubmed:affiliation |
Department of Chemistry, Carnegie Mellon University, Pittsburgh, Pennsylvania 15213, USA.
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| pubmed:publicationType |
Journal Article
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