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rdf:type |
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lifeskim:mentions |
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pubmed:issue |
5
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pubmed:dateCreated |
2002-3-1
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pubmed:abstractText |
The oxidation of a series of para-substituted phenyl methyl sulfides was carried out with several oxo(salen)iron (salen = N,N'-bis(salicylidine)ethylenediaminato) complexes in acetonitrile. The oxo complex [O=Fe(IV)(salen)](*+), generated from an iron(III) [bond] salen complex and iodosylbenzene, effectively oxidizes the organic sulfides to the corresponding sulfoxides. The formation of [O [double bond] Fe(IV)(salen)](*+) as the active oxidant is supported by resonance Raman studies. The kinetic data indicate that the reaction is first-order in the oxidant and fractional-order with respect to sulfide. The observed saturation kinetics of the reaction and spectral data indicate that the substrate binds to the oxidant before the rate-controlling step. The rate constant (k) values for the product formation step determined using Michaelis-Menten kinetics correlate well with Hammett sigma constants, giving reaction constant (rho) values in the range of -0.65 to -1.54 for different oxo(salen)iron complexes. The log k values observed in the oxidation of each aryl methyl sulfide by substituted oxo(salen)iron complexes also correlate with Hammett sigma constants, giving positive rho values. The substituent effect, UV-vis absorption, and EPR spectral studies indicate oxygen atom transfer from the oxidant to the substrate in the rate-determining step.
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pubmed:language |
eng
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pubmed:journal |
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pubmed:citationSubset |
IM
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pubmed:chemical |
http://linkedlifedata.com/resource/pubmed/chemical/Acetonitriles,
http://linkedlifedata.com/resource/pubmed/chemical/Chromium,
http://linkedlifedata.com/resource/pubmed/chemical/Enzymes,
http://linkedlifedata.com/resource/pubmed/chemical/Ethylenediamines,
http://linkedlifedata.com/resource/pubmed/chemical/Ferric Compounds,
http://linkedlifedata.com/resource/pubmed/chemical/Manganese,
http://linkedlifedata.com/resource/pubmed/chemical/Organometallic Compounds,
http://linkedlifedata.com/resource/pubmed/chemical/Ruthenium,
http://linkedlifedata.com/resource/pubmed/chemical/Sulfides,
http://linkedlifedata.com/resource/pubmed/chemical/Sulfoxides,
http://linkedlifedata.com/resource/pubmed/chemical/disalicylaldehyde ethylenediamine
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pubmed:status |
MEDLINE
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pubmed:month |
Mar
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pubmed:issn |
0022-3263
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pubmed:author |
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pubmed:issnType |
Print
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pubmed:day |
8
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pubmed:volume |
67
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pubmed:owner |
NLM
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pubmed:authorsComplete |
Y
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pubmed:pagination |
1506-14
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pubmed:dateRevised |
2006-11-15
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pubmed:meshHeading |
pubmed-meshheading:11871880-Acetonitriles,
pubmed-meshheading:11871880-Catalysis,
pubmed-meshheading:11871880-Chromium,
pubmed-meshheading:11871880-Electron Spin Resonance Spectroscopy,
pubmed-meshheading:11871880-Enzymes,
pubmed-meshheading:11871880-Ethylenediamines,
pubmed-meshheading:11871880-Ferric Compounds,
pubmed-meshheading:11871880-Kinetics,
pubmed-meshheading:11871880-Manganese,
pubmed-meshheading:11871880-Models, Biological,
pubmed-meshheading:11871880-Molecular Structure,
pubmed-meshheading:11871880-Organometallic Compounds,
pubmed-meshheading:11871880-Oxidation-Reduction,
pubmed-meshheading:11871880-Ruthenium,
pubmed-meshheading:11871880-Spectrophotometry, Ultraviolet,
pubmed-meshheading:11871880-Spectrum Analysis, Raman,
pubmed-meshheading:11871880-Sulfides,
pubmed-meshheading:11871880-Sulfoxides
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pubmed:year |
2002
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pubmed:articleTitle |
Iron(III) [bond] Salen complexes as enzyme models: mechanistic study of oxo(salen)iron complexes oxygenation of organic sulfides.
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pubmed:affiliation |
School of Chemistry, Madurai Kamaraj University, Madurai-625 021, India.
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pubmed:publicationType |
Journal Article,
Comparative Study,
Research Support, Non-U.S. Gov't
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