title: Modeling TauD-J: a high-spin nonheme oxoiron(IV) complex with high reactivity toward C-H bonds.
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 Fe(IV)═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, [Fe(IV)(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.
authors: Department of Chemistry and Center for Metals in Biocatalysis, University of Minnesota , Minneapolis, Minnesota 55455, United States.
authors: Achintesh N
authors: AN
authors: Biswas
authors: Mayank
authors: M
authors: Puri
authors: Katlyn K
authors: KK
authors: Meier
authors: Williamson N
authors: WN
authors: Oloo
authors: Gregory T
authors: GT
authors: Rohde
authors: Emile L
authors: EL
authors: Bominaar
authors: Eckard
authors: E
authors: Münck
authors: Lawrence
authors: L
authors: Que
mesh_terms: D040761:Biomimetic Materials / Q000737:chemistry*; D002244:Carbon / Q000737:chemistry*; D006859:Hydrogen / Q000737:chemistry*; D007501:Iron / Q000737:chemistry*; D006899:Mixed Function Oxygenases / Q000378:metabolism*; D008958:Models, Molecular; D008968:Molecular Conformation; D009942:Organometallic Compounds / Q000737:chemistry*; D010084:Oxidation-Reduction
chemical_list: D009942:Organometallic Compounds; D002244:Carbon; D006859:Hydrogen; D007501:Iron; D006899:Mixed Function Oxygenases; C433064:taurine-alpha-ketoglutarate dioxygenase