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Mechanism of catalytic oxygenation of alkanes by halogenated iron porphyrins

Grinstaff, Mark W. and Hill, Michael G. and Labinger, Jay A. and Gray, Harry B. (1994) Mechanism of catalytic oxygenation of alkanes by halogenated iron porphyrins. Science, 264 (5163). pp. 1311-1313. ISSN 0036-8075. https://resolver.caltech.edu/CaltechAUTHORS:20141210-090711278

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Abstract

Halogenation of an iron porphyrin causes severe saddling of the macrocyclic structure and a large positive shift in the iron(III)/(II) redox couple. Although pre-halogenated iron(II) porphyrins such as Fe(TFPPBr_8) [H2TFPPBr_8, β-octabromo-tetrakis(pentafluorophenyl)-porphyrin] are relatively resistant to autoxidation, they rapidly reduce alkyl hydroperoxides. These and related reactivity studies suggest that catalysis of alkane oxygenation by Fe(TFPPBr_8)Cl occurs through a radical-chain mechanism in which the radicals are generated by oxidation and reduction of alkyl hydroperoxides.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1126/science.8191283 DOIArticle
http://www.sciencemag.org/content/264/5163/1311PublisherArticle
http://www.jstor.org/stable/2884078JSTORArticle
ORCID:
AuthorORCID
Labinger, Jay A.0000-0002-1942-9232
Gray, Harry B.0000-0002-7937-7876
Additional Information:© 1994 American Association for the Advancement of Science. Received 28 December 1993; accepted 1 April 1994. We thank J. E. Lyons, P. E. Ellis, W. P. Schaefer, E. R. Birnbaum, and T. Takeuchi for helpful discussions. Supported by the U.S. Department of Energy, Morgantown Energy Technology Center, and the Sun Company. M.W.G. acknowledges an NIH postdoctoral fellowship.
Funders:
Funding AgencyGrant Number
Department of Energy (DOE)UNSPECIFIED
Sun CompanyUNSPECIFIED
NIH Postdoctoral FellowshipUNSPECIFIED
Issue or Number:5163
Record Number:CaltechAUTHORS:20141210-090711278
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20141210-090711278
Official Citation:Mechanism of catalytic oxygenation of alkanes by halogenated iron porphyrins MW Grinstaff, MG Hill, JA Labinger, and HB Gray Science 27 May 1994: 264 (5163), 1311-1313. [DOI:10.1126/science.8191283]
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:52532
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:10 Dec 2014 18:03
Last Modified:22 Nov 2019 09:58

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