Characterization of Mononuclear Non-heme Iron(III)-Superoxo Complex with a Five-Azole Ligand Set.
Reaction of O2 with a high-spin mononuclear iron(II) complex supported by a five-azole donor set yields the corresponding mononuclear non-heme iron(III)-superoxo species, which was characterized by UV/Vis spectroscopy and resonance Raman spectroscopy. (1)H NMR analysis reveals diamagnetic nature of the superoxo complex arising from antiferromagnetic coupling between the spins on the low-spin iron(III) and superoxide. This superoxo species reacts with H-atom donating reagents to give a low-spin iron(III)-hydroperoxo species showing characteristic UV/Vis, resonance Raman, and EPR spectra.
Department of Material and Life Chemistry, Faculty of Engineering, Kanagawa University, Kanagawa-ku, Yokohama, 222-8686 (Japan).
Frédéric
F
Oddon
Department of Material and Life Chemistry, Faculty of Engineering, Kanagawa University, Kanagawa-ku, Yokohama, 222-8686 (Japan).
Yosuke
Y
Chiba
Department of Material and Life Chemistry, Faculty of Engineering, Kanagawa University, Kanagawa-ku, Yokohama, 222-8686 (Japan). jnaka@kanagawa-u.ac.jp.
Jun
J
Nakazawa
Department of Life Science, University of Hyogo, Sayo-cho, Sayo-gun, Hyogo 679-5148 (Japan).
Takehiro
T
Ohta
Department of Life Science, University of Hyogo, Sayo-cho, Sayo-gun, Hyogo 679-5148 (Japan).
Takashi
T
Ogura
Department of Material and Life Chemistry, Faculty of Engineering, Kanagawa University, Kanagawa-ku, Yokohama, 222-8686 (Japan). hikichi@kanagawa-u.ac.jp.
Shiro
S
Hikichi
D001393:Azoles / Q000737:chemistry*; D003035:Cobalt / Q000737:chemistry; D005290:Ferric Compounds / Q000737:chemistry*; D008024:Ligands; D008958:Models, Molecular; D010100:Oxygen / Q000737:chemistry*; D013481:Superoxides / Q000737:chemistry*
D001393:Azoles; D005290:Ferric Compounds; D008024:Ligands; D013481:Superoxides; D003035:Cobalt; D010100:Oxygen
OO activation; bioinorganic chemistry; cobalt; dioxygen ligands; iron