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.
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| 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. | ||||||||||||
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| 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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