Angewandte Chemie International Edition in English

Communication

Full Access

Formation of an Alkylperoxoiron(III) Complex during Oxidations Catalyzed by μ-Oxodiiron(III) Complexes^†

Dr. Stéphane Ménage

L. E. D. S. S., URA 332, Université J. Fourier, BP53X, F-38052 Grenoble Cedex 09 (France). Telefax: Int. code + 76 51 43 82

Search for more papers by this author

Elizabeth C. Wilkinson,

Elizabeth C. Wilkinson

Department of Chemistry, University of Minnesota, Minneapolis, MN 55455 (USA)

Search for more papers by this author

Prof. Lawrence Que Jr.,

Prof. Lawrence Que Jr.

L. E. D. S. S., URA 332, Université J. Fourier, BP53X, F-38052 Grenoble Cedex 09 (France). Telefax: Int. code + 76 51 43 82

Search for more papers by this author

Prof. Marc Fontecave,

Corresponding Author

Prof. Marc Fontecave

L. E. D. S. S., URA 332, Université J. Fourier, BP53X, F-38052 Grenoble Cedex 09 (France). Telefax: Int. code + 76 51 43 82

L. E. D. S. S., URA 332, Université J. Fourier, BP53X, F-38052 Grenoble Cedex 09 (France). Telefax: Int. code + 76 51 43 82Search for more papers by this author

Dr. Stéphane Ménage,

Dr. Stéphane Ménage

L. E. D. S. S., URA 332, Université J. Fourier, BP53X, F-38052 Grenoble Cedex 09 (France). Telefax: Int. code + 76 51 43 82

Search for more papers by this author

Elizabeth C. Wilkinson,

Elizabeth C. Wilkinson

Department of Chemistry, University of Minnesota, Minneapolis, MN 55455 (USA)

Search for more papers by this author

Prof. Lawrence Que Jr.,

Prof. Lawrence Que Jr.

L. E. D. S. S., URA 332, Université J. Fourier, BP53X, F-38052 Grenoble Cedex 09 (France). Telefax: Int. code + 76 51 43 82

Search for more papers by this author

Prof. Marc Fontecave,

Corresponding Author

Prof. Marc Fontecave

L. E. D. S. S., URA 332, Université J. Fourier, BP53X, F-38052 Grenoble Cedex 09 (France). Telefax: Int. code + 76 51 43 82

L. E. D. S. S., URA 332, Université J. Fourier, BP53X, F-38052 Grenoble Cedex 09 (France). Telefax: Int. code + 76 51 43 82Search for more papers by this author

First published: February 3, 1995

https://doi.org/10.1002/anie.199502031

Citations: 71

^†

This work was supported by NATO (M. F. and L. Q., grant CRG-930188) and by the U. S. National Institutes of Health (L. Q., grant GM-38767).

About

PDF

Tools

Share a link

Email
Wechat
Bluesky

Graphical Abstract

UV/Vis, resonance Raman, and EPR spectroscopy served in characterizing the alkylperoxoiron(III) complex 2, an intermediate in the oxidation of alcohols R'OH with alkyl hydroperoxides ROOH catalyzed by μ-oxo complex 1. The results discussed may provide insight for studies of monooxygenases.

References

1(a) D. R. H. Barton, S. D. Bévière, W. Chavasiri, D. Doller, B. Hu, Tetrahedron Lett. 1992, 25, 504.
CAS Web of Science® Google Scholar
(b) L. Saussine, E. Brazil, A. Robine, H. Mimoun, J. Fisher, R. Weiss, J. Am. Chem. Soc. 1985, 107, 3534.
10.1021/ja00298a022
CAS Web of Science® Google Scholar
(c) J. D. Koola, J. K. Kochi, Inorg. Chem. 1987, 26, 908.
10.1021/ic00253a026
CAS Web of Science® Google Scholar
(d) T. Kojima, R. A. Leising, S. Yan, L. Que, Jr., J. Am. Chem. Soc. 1993, 115, 11328.
10.1021/ja00077a035
CAS Web of Science® Google Scholar
2(a) R. H. Fish, M. S. Konings, K. J. Oberhausen, R. H. Fong, W. M. Yu, G. Christou, J. B. Vincent, D. K. Coggin, R. M. Buchanan, Inorg. Chem. 1991, 30, 3002.
10.1021/ic00015a012
CAS Web of Science® Google Scholar
(b) R. A. Leising, J. Kim, M. A. Pérez, L. Que, Jr., J. Am. Chem. Soc. 1993, 115, 618, and references therein.
10.1021/ja00074a017
Web of Science® Google Scholar
3(a) A. C. Rosenzweig, C. A. Frederick, S. J. Lippard, P. Norlund, Nature 1993, 366, 537.
10.1038/366537a0
CAS PubMed Web of Science® Google Scholar
(b) J. Green, H. Dalton, Biochem. J. 1986, 236, 155.
10.1042/bj2360155
CAS PubMed Web of Science® Google Scholar
(c) J. D. Lipscomb, Annu. Rev. Microbiol., in press.
Google Scholar
4 S. Ménage, J.-M. Vincent, C. Lambeaux, G. Chottard, A. Grand, M. Fontecave, Inorg. Chem. 1993, 32, 4766.
10.1021/ic00074a019
CAS Web of Science® Google Scholar
5 Y. Zang, T. E. Elgren, Y. Dong, L. Que, Jr., J. Am. Chem. Soc. 1993, 115, 811.
10.1021/ja00055a076
CAS Web of Science® Google Scholar
6 The reaction of 1 (0.7 mM), 50 equiv of 80% CHP, and 200 equiv benzyl alcohol for 90 s produced 35 equiv benzaldehyde. The yield of the reaction based on the oxidant is 35%.
Google Scholar
7 S. Ahmad, J. D. McCallum, A. K. Shiemke, E. H. Appelman, T. M. Loehr, J. Sanders-Loehr, Inorg. Chem. 1988, 27, 2230.
10.1021/ic00286a006
CAS Web of Science® Google Scholar
8 K. Tajima, T. Edo, K. Ishizy, S. Imaoka, Y. Funae, S. Oka, H. Sakurai, Biochem. Biophys. Res. Commun. 1993, 191, 157.
10.1006/bbrc.1993.1197
CAS PubMed Web of Science® Google Scholar
9 R. M. Burger, J. Peisach, S. B. Horwitz, J. Biol. Chem. 1981, 256, 11636.
10.1016/S0021-9258(19)68452-8
CAS PubMed Web of Science® Google Scholar
10 R. J. Guajardo, S. E. Hudson, S. J. Brown, P. K. Mascharak, J. Am. Chem. Soc. 1993, 115, 7971.
10.1021/ja00071a006
CAS Web of Science® Google Scholar
11 The EPR signal was quantified by double integration with copper sulfate as a standard at 100 K.
Google Scholar
12 The transient species can be generated by using 30 equiv phenol or 4-methylphenol instead of 200 equiv benzyl alcohol. All the phenol was consumed during the oxidation process, and 1,4-benzoquinone and 1,4-hydroquinone were obtained as major products.
Google Scholar
13 This band was not observed in the absence of TBHP, indicating that it does not arise from a phenolate-to-iron(III) charge transfer transition.
Google Scholar

Citing Literature

Volume34, Issue2

February 3, 1995

Pages 203-205

Formation of an Alkylperoxoiron(III) Complex during Oxidations Catalyzed by μ-Oxodiiron(III) Complexes^†

Graphical Abstract

References

Citing Literature

References

Information

About Wiley Online Library

Help & Support

Opportunities

Connect with Wiley

Formation of an Alkylperoxoiron(III) Complex during Oxidations Catalyzed by μ-Oxodiiron(III) Complexes†

Graphical Abstract

References

Citing Literature

References

Related

Information

Formation of an Alkylperoxoiron(III) Complex during Oxidations Catalyzed by μ-Oxodiiron(III) Complexes^†