title: Reversible O-O bond scission of peroxodiiron(III) to high-spin oxodiiron(IV) in dioxygen activation of a diiron center with a bis-tpa dinucleating ligand as a soluble methane monooxygenase model.
abstract: The conversion of peroxodiiron(III) to high-spin S = 2 oxodiiron(IV) via reversible O-O bond scission in a diiron complex with a bis-tpa dinucleating ligand, 6-hpa, has been characterized by elemental analysis; kinetic measurements for alkene epoxidation; cold-spray ionization mass spectrometry; and electronic absorption, Mössbauer, and resonance Raman spectroscopy to gain insight into the O(2) activation mechanism of soluble methane monooxygenases. This is the first synthetic example of a high-spin S = 2 oxodiiron(IV) species that oxidizes alkenes to epoxides efficiently. The bistability of the peroxodiiron(III) and high-spin S = 2 oxodiiron(IV) moieties is the key feature for the reversible O-O bond scission.
authors: Department of Molecular Chemistry and Biochemistry, Doshisha University, Tatara Miyakotani 1-3, Kyotanabe, Kyoto 610-0321, Japan. mkodera@mail.doshisha.ac.jp
authors: Masahito
authors: M
authors: Kodera
authors: Yuka
authors: Y
authors: Kawahara
authors: Yutaka
authors: Y
authors: Hitomi
authors: Takashi
authors: T
authors: Nomura
authors: Takashi
authors: T
authors: Ogura
authors: Yoshio
authors: Y
authors: Kobayashi
mesh_terms: D006861:Hydrogen Peroxide / Q000737:chemistry*; D007501:Iron / Q000737:chemistry*; D008024:Ligands; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000737:chemistry; D010084:Oxidation-Reduction; D010100:Oxygen / Q000737:chemistry*; D010105:Oxygenases / Q000737:chemistry*; D012995:Solubility; D013059:Spectrum Analysis, Raman
chemical_list: D008024:Ligands; D009942:Organometallic Compounds; D006861:Hydrogen Peroxide; D007501:Iron; D010105:Oxygenases; C021555:methane monooxygenase; D010100:Oxygen