title: Characterization of a high-spin non-heme Fe(III)-OOH intermediate and its quantitative conversion to an Fe(IV)═O complex.
abstract: We have generated a high-spin Fe(III)-OOH complex supported by tetramethylcyclam via protonation of its conjugate base and characterized it in detail using various spectroscopic methods. This Fe(III)-OOH species can be converted quantitatively to an Fe(IV)═O complex via O-O bond cleavage; this is the first example of such a conversion. This conversion is promoted by two factors: the strong Fe(III)-OOH bond, which inhibits Fe-O bond lysis, and the addition of protons, which facilitates O-O bond cleavage. This example provides a synthetic precedent for how O-O bond cleavage of high-spin Fe(III)-peroxo intermediates of non-heme iron enzymes may be promoted.
authors.affiliation: Department of Chemistry and Center for Metals in Biocatalysis, University of Minnesota, Minneapolis, Minnesota 55455, USA.
authors.forename: Feifei
authors.initials: F
authors.lastname: Li
authors.forename: Katlyn K
authors.initials: KK
authors.lastname: Meier
authors.forename: Matthew A
authors.initials: MA
authors.lastname: Cranswick
authors.forename: Mrinmoy
authors.initials: M
authors.lastname: Chakrabarti
authors.forename: Katherine M
authors.initials: KM
authors.lastname: Van Heuvelen
authors.forename: Eckard
authors.initials: E
authors.lastname: Münck
authors.forename: Lawrence
authors.initials: L
authors.lastname: Que
mesh_terms: D006418:Heme / Q000737:chemistry; D007501:Iron / Q000737:chemistry*; D015394:Molecular Structure; D009942:Organometallic Compounds; D010100:Oxygen / Q000737:chemistry*
chemical_list: D009942:Organometallic Compounds; D006418:Heme; D007501:Iron; D010100:Oxygen