1. Combining Structural with Functional Model Properties in Iron Synthetic Analogue Complexes for the Active Site in Rabbit Lipoxygenase
- Author
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Matina Eloïse de Waal Malefijt, Hans-Jörg Krüger, Johannes E. M. N. Klein, Markus Schmitz, Harald Kelm, Thorsten Bonck, Christian Rauber, Emiel Dobbelaar, Stratingh Institute of Chemistry, and Molecular Inorganic Chemistry
- Subjects
Molecular Structure ,biology ,Ligand ,Chemistry ,Lipoxygenase ,Active site ,General Chemistry ,Hydrogen atom abstraction ,Biochemistry ,Catalysis ,Ferrous ,Electron transfer ,Colloid and Surface Chemistry ,Catalytic Domain ,Polymer chemistry ,biology.protein ,medicine ,Animals ,Ferric ,Molecule ,Reactivity (chemistry) ,Rabbits ,Iron Compounds ,medicine.drug - Abstract
Iron complexes that model the structural and functional properties of the active iron site in rabbit lipoxygenase are described. The ligand sphere of the mononuclear pseudo-octahedral cis-(carboxylato)(hydroxo)iron(III) complex, which is completed by a tetraazamacrocyclic ligand, reproduces the first coordination shell of the active site in the enzyme. In addition, two corresponding iron(II) complexes are presented that differ in the coordination of a water molecule. In their structural and electronic properties, both the (hydroxo)iron(III) and the (aqua)iron(II) complex reflect well the only two essential states found in the enzymatic mechanism of peroxidation of polyunsaturated fatty acids. Furthermore, the ferric complex is shown to undergo hydrogen atom abstraction reactions with O-H and C-H bonds of suitable substrates, and the bond dissociation free energy of the coordinated water ligand of the ferrous complex is determined to be 72.4 kcal·mol-1. Theoretical investigations of the reactivity support a concerted proton-coupled electron transfer mechanism in close analogy to the initial step in the enzymatic mechanism. The propensity of the (hydroxo)iron(III) complex to undergo H atom abstraction reactions is the basis for its catalytic function in the aerobic peroxidation of 2,4,6-tri(tert-butyl)phenol and its role as a radical initiator in the reaction of dihydroanthracene with oxygen.
- Published
- 2021