ArticleJournal of the American Chemical Society2013
Acid-induced mechanism change and overpotential decrease in dioxygen reduction catalysis with a dinuclear copper complex.
Article in Journal of the American Chemical Society, 2013. The graph could read no effect estimate from its abstract, so it casts no vote on the map. Cited by 11 papers.
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Who cites it
11 citing papers in PubMed, 63 citations in OpenAlex.
- Coordination Variations within Binuclear Copper Dioxygen-Derived (Hydro)Peroxo and Superoxo Species; Influences upon Thermodynamic and Electronic Properties.Journal of the American Chemical Society · 2024Article
- Evidence of Sulfur Non-Innocence in [CoAngewandte Chemie (International ed. in English) · 2023Article
- Production of chlorine-containing functional group doped graphene powders using Yucel's method as anode materials for Li-ion batteries.RSC advances · 2021Article
- Ligand Identity-Induced Generation of Enhanced Oxidative Hydrogen Atom Transfer Reactivity for a CuJournal of the American Chemical Society · 2019Article
- Mononuclear Manganese(III) Superoxo Complexes: Synthesis, Characterization, and Reactivity.Inorganic chemistry · 2019Article
- Copper-Promoted Functionalization of Organic Molecules: from Biologically Relevant Cu/OChemical reviews · 2019Review
- Copper-Oxygen Complexes Revisited: Structures, Spectroscopy, and Reactivity.Chemical reviews · 2017Review
- Photocatalytic Oxygenation of Substrates by Dioxygen with Protonated Manganese(III) Corrolazine.Inorganic chemistry · 2016Article
- Laser-Induced Dynamics of Peroxodicopper(II) Complexes Vary with the Ligand Architecture. One-Photon Two-Electron O2 Ejection and Formation of Mixed-Valent Cu(I)Cu(II)-Superoxide Intermediates.Journal of the American Chemical Society · 2015Article
- Catalytic two-electron reduction of dioxygen catalysed by metal-free [14]triphyrin(2.1.1).Chemical science · 2015Article
- Lewis acid-induced change from four- to two-electron reduction of dioxygen catalyzed by copper complexes using scandium triflate.Journal of the American Chemical Society · 2015Article
Corrections and comments
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Authors and funding
6 authors at 2 institutions in 3 countries.
Funding
Abstract
Catalytic four-electron reduction of O2 by ferrocene (Fc) and 1,1'-dimethylferrocene (Me2Fc) occurs efficiently with a dinuclear copper(II) complex [Cu(II)2(XYLO)(OH)](2+) (1), where XYLO is a m-xylene-linked bis[(2-(2-pyridyl)ethyl)amine] dinucleating ligand with copper-bridging phenolate moiety], in the presence of perchloric acid (HClO4) in acetone at 298 K. The hydroxide and phenoxo group in [Cu(II)2(XYLO)(OH)](2+) (1) undergo protonation with HClO4 to produce [Cu(II)2(XYLOH)](4+) (2) where the two copper centers become independent and the reduction potential shifts from -0.68 V vs SCE in the absence of HClO4 to 0.47 V; this makes possible the use of relatively weak one-electron reductants such as Fc and Me2Fc, significantly reducing the effective overpotential in the catalytic O2-reduction reaction. The mechanism of the reaction has been clarified on the basis of kinetic studies on the overall catalytic reaction as well as each step in the catalytic cycle and also by low-temperature detection of intermediates. The O2-binding to the fully reduced complex [Cu(I)2(XYLOH)](2+) (3) results in the reversible formation of the hydroperoxo complex ([Cu(II)2(XYLO)(OOH)](2+)) (4), followed by proton-coupled electron-transfer (PCET) reduction to complete the overall O2-to-2H2O catalytic conversion.
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