title: A mononuclear non-heme manganese(IV)-oxo complex binding redox-inactive metal ions.
abstract: Redox-inactive metal ions play pivotal roles in regulating the reactivities of high-valent metal-oxo species in a variety of enzymatic and chemical reactions. A mononuclear non-heme Mn(IV)-oxo complex bearing a pentadentate N5 ligand has been synthesized and used in the synthesis of a Mn(IV)-oxo complex binding scandium ions. The Mn(IV)-oxo complexes were characterized with various spectroscopic methods. The reactivities of the Mn(IV)-oxo complex are markedly influenced by binding of Sc(3+) ions in oxidation reactions, such as a ~2200-fold increase in the rate of oxidation of thioanisole (i.e., oxygen atom transfer) but a ~180-fold decrease in the rate of C-H bond activation of 1,4-cyclohexadiene (i.e., hydrogen atom transfer). The present results provide the first example of a non-heme Mn(IV)-oxo complex binding redox-inactive metal ions that shows a contrasting effect of the redox-inactive metal ions on the reactivities of metal-oxo species in the oxygen atom transfer and hydrogen atom transfer reactions.
authors: Department of Bioinspired Science, Chemistry and Nano Science, Ewha Womans University, Seoul 120-750, Korea.
authors: Junying
authors: J
authors: Chen
authors: Yong-Min
authors: YM
authors: Lee
authors: Katherine M
authors: KM
authors: Davis
authors: Xiujuan
authors: X
authors: Wu
authors: Mi Sook
authors: MS
authors: Seo
authors: Kyung-Bin
authors: KB
authors: Cho
authors: Heejung
authors: H
authors: Yoon
authors: Young Jun
authors: YJ
authors: Park
authors: Shunichi
authors: S
authors: Fukuzumi
authors: Yulia N
authors: YN
authors: Pushkar
authors: Wonwoo
authors: W
authors: Nam
mesh_terms: D004578:Electron Spin Resonance Spectroscopy; D004583:Electrons; D007202:Indicators and Reagents; D008345:Manganese / Q000737:chemistry*; D008670:Metals / Q000737:chemistry*; D008958:Models, Molecular; D008968:Molecular Conformation; D010084:Oxidation-Reduction; D010100:Oxygen / Q000737:chemistry; D011522:Protons; D012538:Scandium / Q000737:chemistry; D021241:Spectrometry, Mass, Electrospray Ionization; D013056:Spectrophotometry, Ultraviolet; D014961:X-Ray Diffraction
chemical_list: D007202:Indicators and Reagents; D008670:Metals; D011522:Protons; D008345:Manganese; D010100:Oxygen; D012538:Scandium