title: Nuclear resonance vibrational spectroscopic and computational study of high-valent diiron complexes relevant to enzyme intermediates.
abstract: High-valent intermediates of binuclear nonheme iron enzymes are structurally unknown despite their importance for understanding enzyme reactivity. Nuclear resonance vibrational spectroscopy combined with density functional theory calculations has been applied to structurally well-characterized high-valent mono- and di-oxo bridged binuclear Fe model complexes. Low-frequency vibrational modes of these high-valent diiron complexes involving Fe motion have been observed and assigned. These are independent of Fe oxidation state and show a strong dependence on spin state. It is important to note that they are sensitive to the nature of the Fe2 core bridges and provide the basis for interpreting parallel nuclear resonance vibrational spectroscopy data on the high-valent oxo intermediates in the binuclear nonheme iron enzymes.
authors.affiliation: Department of Chemistry, Stanford University, Stanford, CA 94305, USA.
authors.forename: Kiyoung
authors.initials: K
authors.lastname: Park
authors.forename: Caleb B
authors.initials: CB
authors.lastname: Bell
authors.forename: Lei V
authors.initials: LV
authors.lastname: Liu
authors.forename: Dong
authors.initials: D
authors.lastname: Wang
authors.forename: Genqiang
authors.initials: G
authors.lastname: Xue
authors.forename: Yeonju
authors.initials: Y
authors.lastname: Kwak
authors.forename: Shaun D
authors.initials: SD
authors.lastname: Wong
authors.forename: Kenneth M
authors.initials: KM
authors.lastname: Light
authors.forename: Jiyong
authors.initials: J
authors.lastname: Zhao
authors.forename: E Ercan
authors.initials: EE
authors.lastname: Alp
authors.forename: Yoshitaka
authors.initials: Y
authors.lastname: Yoda
authors.forename: Makina
authors.initials: M
authors.lastname: Saito
authors.forename: Yasuhiro
authors.initials: Y
authors.lastname: Kobayashi
authors.forename: Takehiro
authors.initials: T
authors.lastname: Ohta
authors.forename: Makoto
authors.initials: M
authors.lastname: Seto
authors.forename: Lawrence
authors.initials: L
authors.lastname: Que
authors.forename: Edward I
authors.initials: EI
authors.lastname: Solomon
mesh_terms: D018360:Crystallography, X-Ray; D004798:Enzymes / Q000737:chemistry* / Q000378:metabolism; D005290:Ferric Compounds / Q000737:chemistry* / Q000378:metabolism; D008956:Models, Chemical; D015394:Molecular Structure; D010084:Oxidation-Reduction; D015204:Spectroscopy, Mossbauer / Q000379:methods*; D014732:Vibration
chemical_list: D004798:Enzymes; D005290:Ferric Compounds