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Published Online October 27, 2005
Science DOI: 10.1126/science.1119092

Reports

Submitted on August 19, 2005
Accepted on October 11, 2005

A Thiolate-Ligated Nonheme Oxoiron(IV) Complex Relevant to Cytochrome P450

Michael R. Bukowski 1, Kevin D. Koehntop 2, Audria Stubna 3, Emile L. Bominaar 3, Jason A. Halfen 4*, Eckard Münck 3*, Wonwoo Nam 5, Lawrence Que Jr 6*

1 Department of Chemistry and Center for Metals in Biocatalysis, University of Minnesota, Minneapolis, MN 55455, USA; Present address: Penn State Altoona, 3000 Ivyside Park, Altoona, PA 16601, USA.
2 Department of Chemistry and Center for Metals in Biocatalysis, University of Minnesota, Minneapolis, MN 55455, USA; Present address: The Scripps Research Institute, La Jolla, CA 92037, USA.
3 Department of Chemistry, Carnegie Mellon University, Pittsburgh, PA 15213, USA.
4 Department of Chemistry, University of Wisconsin Eau Claire, Eau Claire, WI 54702, USA.
5 Department of Chemistry, Division of Nano Sciences, and Center for Biomimetic Systems, Ewha Womans University, Seoul 120-750, Korea.
6 Department of Chemistry and Center for Metals in Biocatalysis, University of Minnesota, Minneapolis, MN 55455, USA.

* To whom correspondence should be addressed.
Jason A. Halfen , E-mail: halfenja{at}uwec.edu
Eckard Münck , E-mail: emunck{at}cmu.edu
Lawrence Que Jr , E-mail: que{at}chem.umn.edu

Thiolate-ligated oxoiron(IV) centers are postulated as the key oxidants in the catalytic cycles of oxygen activating cytochrome P450 and related enzymes. Despite considerable synthetic efforts, chemists have not succeeded in synthesizing an appropriate model complex. Here we report the synthesis and spectroscopic characterization of [FeIV(O)(TMCS)]+ where TMCS is a pentadentate ligand that provides a square pyramidal N4(SR)apical ligand environment about the iron center similar to that of cytochrome P450. The rigidity of the ligand framework stabilizes the thiolate in an oxidizing environment. Reactivity studies suggest that thiolate coordination favors H-atom abstraction chemistry over O-atom transfer pathways in the presence of reducing substrates.


THIS ARTICLE HAS BEEN CITED BY OTHER ARTICLES:
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Science. ISSN 0036-8075 (print), 1095-9203 (online)