title: A nonheme iron(II) complex that models the redox cycle of lipoxygenase.
abstract: The air-stable complex [Fe(6-Me3-TPA) (O2CAr)]+ [1; 6-Me3-TPA = tris(6-methyl-2-pyridylmethyl)amine] has been synthesized as a model for the iron(II) site of lipoxygenase. This iron(II) complex reacts with 0.5 equiv ROOH to form a yellow species, which has been formulated as [FeIII(OH)(6-Me3-TPA) (O2CAr)]+ (2) by electrospray mass spectrometry. Addition of more ROOH converts 2 into a purple species, which is characterized by electrospray ionization mass spectrometry and resonance Raman spectroscopy as [FeIII(OOR)(6-Me3-TPA)(O2CAr)]+. The purple species is metastable and decomposes via Fe-O bond homolysis to regenerate the starting iron(II) complex. These metal-centered transformations parallel the changes observed for lipoxygenase in its reaction with its product hydroperoxide.
authors: Department of Chemistry and Center for Metals in Biocatalysis, University of Minnesota, 207 Pleasant St. S.E., Minneapolis, MN 55455, USA.
authors: J
authors: J
authors: Kim
authors: Y
authors: Y
authors: Zang
authors: M
authors: M
authors: Costas
authors: R G
authors: RG
authors: Harrison
authors: E C
authors: EC
authors: Wilkinson
authors: L
authors: L
authors: Que
mesh_terms: D003510:Cyclohexanes / Q000737:chemistry; D053138:Cyclohexenes; D005296:Ferrous Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D008084:Lipoxygenase / Q000737:chemistry* / Q000378:metabolism; D018716:Molecular Mimicry; D015394:Molecular Structure; D010084:Oxidation-Reduction; D021241:Spectrometry, Mass, Electrospray Ionization; D013059:Spectrum Analysis, Raman
chemical_list: D003510:Cyclohexanes; D053138:Cyclohexenes; D005296:Ferrous Compounds; C436299:benzoatotris(6-methyl-2-pyridylmethyl)amineiron(II); C048401:1,4-cyclohexadiene; D008084:Lipoxygenase