Modeling TauD- J: A high-spin nonheme oxoiron(IV) complex with high reactivity toward C-H bonds

Achintesh N. Biswas, Mayank Puri, Katlyn K. Meier, Williamson N Oloo, Gregory T. Rohde, Emile L. Bominaar, Eckard Münck, Larry Que

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95 Scopus citations

Abstract

High-spin oxoiron(IV) species are often implicated in the mechanisms of nonheme iron oxygenases, their C-H bond cleaving properties being attributed to the quintet spin state. However, the few available synthetic S = 2 FeIV=O complexes supported by polydentate ligands do not cleave strong C-H bonds. Herein we report the characterization of a highly reactive S = 2 complex, [FeIV(O)(TQA)(NCMe)]2+ (2) (TQA = tris(2-quinolylmethyl)amine), which oxidizes both C-H and C=C bonds at -40 °C. The oxidation of cyclohexane by 2 occurs at a rate comparable to that of the oxidation of taurine by the TauD-J enzyme intermediate after adjustment for the different temperatures of measurement. Moreover, compared with other S = 2 complexes characterized to date, the spectroscopic properties of 2 most closely resemble those of TauD-J. Together these features make 2 the best electronic and functional model for TauD-J to date.

Original languageEnglish (US)
Pages (from-to)2428-2431
Number of pages4
JournalJournal of the American Chemical Society
Volume137
Issue number7
DOIs
StatePublished - Feb 25 2015

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