title: Spectroscopic and quantum chemical characterization of the electronic structure and bonding in a non-heme FeIV[double bond]O complex.
abstract: High valent FeIV=O species are key intermediates in the catalytic cycles of many mononuclear non-heme iron enzymes involving the binding and activation of dioxygen. Using variable temperature magnetic circular dichroism (VT MCD) spectroscopy and experimentally calibrated density functional calculations, we are able to present the first detailed description of the electronic structure of a non-heme FeIV=O S = 1 complex. These studies define the nature of the FeIV=O bond and present the basis for understanding high-valent oxygen intermediates in non-heme iron enzymes.
authors.affiliation: Department of Chemistry, Stanford University, Stanford, California 94305, USA.
authors.forename: Andrea
authors.initials: A
authors.lastname: Decker
authors.forename: Jan-Uwe
authors.initials: JU
authors.lastname: Rohde
authors.forename: Lawrence
authors.initials: L
authors.lastname: Que
authors.forename: Edward I
authors.initials: EI
authors.lastname: Solomon
mesh_terms: D002942:Circular Dichroism; D004583:Electrons; D007501:Iron / Q000737:chemistry*; D008024:Ligands; D008968:Molecular Conformation; D019159:Nonheme Iron Proteins / Q000737:chemistry*; D010100:Oxygen / Q000737:chemistry*; D011789:Quantum Theory; D013696:Temperature
chemical_list: D008024:Ligands; D019159:Nonheme Iron Proteins; D007501:Iron; D010100:Oxygen