Biochemistry: A thiolate-ligated nonheme oxoiron(IV) complex relevant to cytochrome P450

Michael R. Bukowski, Kevin D. Koehntop, Audria Stubna, Emile L. Bominaar, Jason A. Halfen, Eckard Münck, Wonwoo Nam, Lawrence Que

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200 Scopus citations

Abstract

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 N 4(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.

Original languageEnglish (US)
Pages (from-to)1000-1002
Number of pages3
JournalScience
Volume310
Issue number5750
DOIs
StatePublished - Nov 11 2005

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