title: Characterization of a paramagnetic mononuclear nonheme iron-superoxo complex.
abstract: O2 bubbling into a THF solution of Fe(II)(BDPP) (1) at -80 °C generates a reversible bright yellow adduct 2. Characterization by resonance Raman and Mössbauer spectroscopy provides complementary insights into the nature of 2. The former shows a resonance-enhanced vibration at 1125 cm(-1), which can be assigned to the ν(O-O) of a bound superoxide, while the latter reveals the presence of a high-spin iron(III) center that is exchange-coupled to the superoxo ligand, like the Fe(III)-O2(-) pair found for the O2 adduct of 4-nitrocatechol-bound homoprotocatechuate 2,3-dioxygenase. Lastly, 2 oxidizes dihydroanthracene to anthracene, supporting the notion that Fe(III)-O2(-) species can carry out H atom abstraction from a C-H bond to initiate the 4-electron oxidation of substrates proposed for some nonheme iron enzymes.
authors.affiliation: Department of Chemistry, National Taiwan Normal University , Taipei 11677, Taiwan (ROC).
authors.forename: Chien-Wei
authors.initials: CW
authors.lastname: Chiang
authors.forename: Scott T
authors.initials: ST
authors.lastname: Kleespies
authors.forename: Heather D
authors.initials: HD
authors.lastname: Stout
authors.forename: Katlyn K
authors.initials: KK
authors.lastname: Meier
authors.forename: Po-Yi
authors.initials: PY
authors.lastname: Li
authors.forename: Emile L
authors.initials: EL
authors.lastname: Bominaar
authors.forename: Lawrence
authors.initials: L
authors.lastname: Que
authors.forename: Eckard
authors.initials: E
authors.lastname: Münck
authors.forename: Way-Zen
authors.initials: WZ
authors.lastname: Lee
mesh_terms: D007501:Iron / Q000737:chemistry*; D059346:Magnets / Q000737:chemistry*; D008958:Models, Molecular; D008968:Molecular Conformation; D009942:Organometallic Compounds / Q000737:chemistry*; D010100:Oxygen / Q000737:chemistry*
chemical_list: D009942:Organometallic Compounds; D007501:Iron; D010100:Oxygen