fulltext.study @t Gmail

Oxidations of cycloalkanes and benzene by hydrogen peroxide catalyzed by an {FeIIIN2S2} centre

Paper ID Volume ID Publish Year Pages File Format Full-Text
43086 45954 2009 6 PDF Available
Title
Oxidations of cycloalkanes and benzene by hydrogen peroxide catalyzed by an {FeIIIN2S2} centre
Abstract

The ironIII complex [Fe(gma)(PBu3)] [H2(gma) = glyoxal-bis(2-mercaptoanil)], bearing an {FeN2S2} centre, was found to act as a selective catalyst or catalyst precursor towards the oxidation, under mild conditions, of (i) cycloalkanes (cyclopentane and cyclohexane) to the corresponding cyclic alcohols and cyclic ketones, and (ii) benzene to phenol, by aqueous H2O2 in CH3CN and in the presence of pyrazinecarboxylic acid (Hpca) or nitric acid as additives. The system exhibits a good selectivity towards the alcohols (typically ca. 90% upon deoxygenation of the formed cycloalkyl hydroperoxides by PPh3). The influence of various factors, such as temperature, amounts of reagents and reaction time, were investigated in a systematic way, and overall yields of alcohols and ketones up to 17% and of phenol up to 20% were achieved. Catalyst turnover numbers (TONs) of 490, 415 and 110 were obtained in the oxidation of cyclopentane, cyclohexane and phenol, respectively. The turnover frequency (TOF) is comparable with those of alkane monooxygenases. The reactions proceed via both oxygen- and carbon-radicals as shown by experiments with radical traps.

Graphical abstractAn iron(III) complex bearing an {FeN2S2} centre was found to act as an efficient catalyst (TONs up to 490) for the oxidation, under mild conditions, of cycloalkanes and benzene by aqueous H2O2 in CH3CN, in the presence of pyrazinecarboxylic acid or nitric acid.Figure optionsDownload full-size imageDownload as PowerPoint slide

Keywords
Iron catalyst; Hydrogen peroxide; N,S ligands; Alkanes; C–H activation
First Page Preview
Oxidations of cycloalkanes and benzene by hydrogen peroxide catalyzed by an {FeIIIN2S2} centre
Get Full-Text Now
Don't Miss Today's Special Offer
Price was $35.95
You save - $31
Price after discount Only $4.95
100% Money Back Guarantee
Full-text PDF Download
Online Support
Any Questions? feel free to contact us
Publisher
Database: Elsevier - ScienceDirect
Journal: Applied Catalysis A: General - Volume 353, Issue 1, 31 January 2009, Pages 107–112
Authors
, , , , ,
Subjects
Physical Sciences and Engineering Chemical Engineering Catalysis
Get Full-Text Now
Don't Miss Today's Special Offer
Price was $35.95
You save - $31
Price after discount Only $4.95
100% Money Back Guarantee
Full-text PDF Download
Online Support
Any Questions? feel free to contact us