ArticleJournal of the American Chemical Society2012
Factors that control catalytic two- versus four-electron reduction of dioxygen by copper complexes.
Article in Journal of the American Chemical Society, 2012. The graph could read no effect estimate from its abstract, so it casts no vote on the map. Cited by 18 papers.
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Who cites it
18 citing papers in PubMed, 93 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
- Strategies for Sustainable Production of Hydrogen Peroxide via Oxygen Reduction Reaction: From Catalyst Design to Device Setup.Nano-micro letters · 2023Review
- Mechanistic Investigations into the Selective Reduction of Oxygen by a Multicopper Oxidase T3 Site-Inspired Dicopper Complex.ACS catalysis · 2023Article
- Electrocatalytic Production of Hydrogen Peroxide Enabled by Post-Synthetic Modification of a Self-Assembled Porphyrin Cube.Inorganic chemistry frontiers · 2023Article
- Electrocatalytic Oxygen Reduction to Produce Hydrogen Peroxide: Rational Design from Single-Atom Catalysts to Devices.Electrochemical energy reviews · 2022Review
- A merged copper(I/II) cluster isolated from Glaser coupling.Nature communications · 2019Article
- Ligand Identity-Induced Generation of Enhanced Oxidative Hydrogen Atom Transfer Reactivity for a CuJournal of the American Chemical Society · 2019Article
- Reversible uptake of molecular oxygen by heteroligand Co(II)-L-α-amino acid-imidazole systems: equilibrium models at full mass balance.Chemistry Central journal · 2017Article
- 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
- Reversible Oxygenation of α-Amino Acid-Cobalt(II) Complexes.Bioinorganic chemistry and applications · 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
- Di- and Trinuclear Mixed-Valence Copper Amidinate Complexes from Reduction of Iodine.Inorganic chemistry · 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
- Enhanced catalytic four-electron dioxygen (O2) and two-electron hydrogen peroxide (H2O2) reduction with a copper(II) complex possessing a pendant ligand pivalamido group.Journal of the American Chemical Society · 2013Article
- Acid-induced mechanism change and overpotential decrease in dioxygen reduction catalysis with a dinuclear copper complex.Journal of the American Chemical Society · 2013Article
- Temperature-independent catalytic two-electron reduction of dioxygen by ferrocenes with a copper(II) tris[2-(2-pyridyl)ethyl]amine catalyst in the presence of perchloric acid.Journal of the American Chemical Society · 2013Article
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Authors and funding
6 authors at 3 institutions in 3 countries.
Funding
Abstract
The selective two-electron reduction of O(2) by one-electron reductants such as decamethylferrocene (Fc*) and octamethylferrocene (Me(8)Fc) is efficiently catalyzed by a binuclear Cu(II) complex [Cu(II)(2)(LO)(OH)](2+) (D1) {LO is a binucleating ligand with copper-bridging phenolate moiety} in the presence of trifluoroacetic acid (HOTF) in acetone. The protonation of the hydroxide group of [Cu(II)(2)(LO)(OH)](2+) with HOTF to produce [Cu(II)(2)(LO)(OTF)](2+) (D1-OTF) makes it possible for this to be reduced by 2 equiv of Fc* via a two-step electron-transfer sequence. Reactions of the fully reduced complex [Cu(I)(2)(LO)](+) (D3) with O(2) in the presence of HOTF led to the low-temperature detection of the absorption spectra due to the peroxo complex [Cu(II)(2)(LO)(OO)] (D) and the protonated hydroperoxo complex [Cu(II)(2)(LO)(OOH)](2+) (D4). No further Fc* reduction of D4 occurs, and it is instead further protonated by HOTF to yield H(2)O(2) accompanied by regeneration of [Cu(II)(2)(LO)(OTF)](2+) (D1-OTF), thus completing the catalytic cycle for the two-electron reduction of O(2) by Fc*. Kinetic studies on the formation of Fc*(+) under catalytic conditions as well as for separate examination of the electron transfer from Fc* to D1-OTF reveal there are two important reaction pathways operating. One is a rate-determining second reduction of D1-OTF, thus electron transfer from Fc* to a mixed-valent intermediate [Cu(II)Cu(I)(LO)](2+) (D2), which leads to [Cu(I)(2)(LO)](+) that is coupled with O(2) binding to produce [Cu(II)(2)(LO)(OO)](+) (D). The other involves direct reaction of O(2) with the mixed-valent compound D2 followed by rapid Fc* reduction of a putative superoxo-dicopper(II) species thus formed, producing D.
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