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Originally published in Science Express on 27 October 2005
Science 11 November 2005:
Vol. 310. no. 5750, pp. 1000 - 1002
DOI: 10.1126/science.1119092
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Reports

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

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

Thiolate-ligated oxoiron(IV) centers are postulated to be the key oxidants in the catalytic cycles of oxygen-activating cytochrome P450 and related enzymes. Despite considerable synthetic efforts, chemists have not succeeded in preparing 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, where SR is thiolate, ligand environment about the iron center, which is 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 hydrogen-atom abstraction chemistry over oxygen-atom transfer pathways in the presence of reducing substrates.

1 Department of Chemistry and Center for Metals in Biocatalysis, University of Minnesota, Minneapolis, MN 55455, USA.
2 Department of Chemistry, Carnegie Mellon University, Pittsburgh, PA 15213, USA.
3 Department of Chemistry, University of Wisconsin Eau Claire, Eau Claire, WI 54702, USA.
4 Department of Chemistry, Division of Nano Sciences, and Center for Biomimetic Systems, Ewha Womans University, Seoul 120-750, Korea.

* Present address: Penn State Altoona, 3000 Ivyside Park, Altoona, PA 16601, USA.

{dagger} Present address: The Scripps Research Institute, La Jolla, CA 92037, USA.

{ddagger} To whom correspondence should be addressed. Email: halfenja{at}uwec.edu (J.A.H.); emunck{at}cmu.edu (E.M.); que{at}chem.umn.edu (L.Q.)

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