ArticleJournal of the American Chemical Society2016
Peroxo and Superoxo Moieties Bound to Copper Ion: Electron-Transfer Equilibrium with a Small Reorganization Energy.
Article in Journal of the American Chemical Society, 2016. The graph could read no effect estimate from its abstract, so it casts no vote on the map. Cited by 19 papers.
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Who cites it
19 citing papers in PubMed.
- Ligand Radicals Tune LPMO Activity in Model Complex.Inorganic chemistry · 2026Article
- Controlling outer-sphere solvent reorganization energy to turn on or off the function of artificial metalloenzymes.Nature communications · 2025Article
- Dioxygenase Chemistry in Nucleophilic Aldehyde Deformylations Utilizing Dicopper OJournal of the American Chemical Society · 2024Article
- Copper-oxygen adducts: new trends in characterization and properties towards C-H activation.Chemical science · 2024Review
- 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
- Ligand-Copper(I) Primary OAccounts of chemical research · 2023Article
- Macrocycle-Induced Modulation of Internuclear Interactions in Homobimetallic Complexes.Inorganic chemistry · 2022Article
- A designed second-sphere hydrogen-bond interaction that critically influences the O-O bond activation for heterolytic cleavage in ferric iron-porphyrin complexes.Chemical science · 2020Article
- Low Reorganization Energy for Electron Self-Exchange by a Formally Copper(III,II) Redox Couple.Inorganic chemistry · 2019Article
- Long non-coding RNA HOTAIR promotes cancer cell energy metabolism in pancreatic adenocarcinoma by upregulating hexokinase-2.Oncology letters · 2019Article
- Ligand Identity-Induced Generation of Enhanced Oxidative Hydrogen Atom Transfer Reactivity for a CuJournal of the American Chemical Society · 2019Article
- Copper-Promoted Functionalization of Organic Molecules: from Biologically Relevant Cu/OChemical reviews · 2019Review
- Synthetic Fe/Cu Complexes: Toward Understanding Heme-Copper Oxidase Structure and Function.Chemical reviews · 2018Review
- Intramolecular Hydrogen Bonding Enhances Stability and Reactivity of Mononuclear Cupric Superoxide Complexes.Journal of the American Chemical Society · 2018Article
- MicroRNA-214 inhibits the proliferation and invasion of lung carcinoma cells by targeting JAK1.American journal of translational research · 2018Article
- Direct Determination of Electron-Transfer Properties of Dicopper-Bound Reduced Dioxygen Species by a Cryo-Spectroelectrochemical Approach.Chemistry (Weinheim an der Bergstrasse, Germany) · 2017Article
- Activation of dioxygen by copper metalloproteins and insights from model complexes.Journal of biological inorganic chemistry : JBIC : a publication of the Society of Biological Inorganic Chemistry · 2017Review
- A Peroxynitrite Dicopper Complex: Formation via Cu-NO and Cu-OJournal of the American Chemical Society · 2016Article
- Copper(I)-Dioxygen Adducts and Copper Enzyme Mechanisms.Israel journal of chemistry · 2016Article
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Authors and funding
8 authors.
Funding
Abstract
Oxygenation of [Cu2(UN-O(-))(DMF)](2+) (1), a structurally characterized dicopper Robin-Day class I mixed-valent Cu(II)Cu(I) complex, with UN-O(-) as a binucleating ligand and where dimethylformamide (DMF) binds to the Cu(II) ion, leads to a superoxo-dicopper(II) species [Cu(II)2(UN-O(-))(O2(•-))](2+) (2). The formation kinetics provide that kon = 9 × 10(-2) M(-1) s(-1) (-80 °C), ΔH(‡) = 31.1 kJ mol(-1) and ΔS(‡) = -99.4 J K(-1) mol(-1) (from -60 to -90 °C data). Complex 2 can be reversibly reduced to the peroxide species [Cu(II)2(UN-O(-))(O2(2-))](+) (3), using varying outer-sphere ferrocene or ferrocenium redox reagents. A Nernstian analysis could be performed by utilizing a monodiphenylamine substituted ferrocenium salt to oxidize 3, leading to an equilibrium mixture with Ket = 5.3 (-80 °C); a standard reduction potential for the superoxo-peroxo pair is calculated to be E° = +130 mV vs SCE. A literature survey shows that this value falls into the range of biologically relevant redox reagents, e.g., cytochrome c and an organic solvent solubilized ascorbate anion. Using mixed-isotope resonance Raman (rRaman) spectroscopic characterization, accompanied by DFT calculations, it is shown that the superoxo complex consists of a mixture of μ-1,2- (2(1,2)) and μ-1,1- (2(1,1)) isomers, which are in rapid equilibrium. The electron transfer process involves only the μ-1,2-superoxo complex [Cu(II)2(UN-O(-))(μ-1,2-O2(•-))](2+) (2(1,2)) and μ-1,2-peroxo structures [Cu(II)2(UN-O(-))(O2(2-))](+) (3) having a small bond reorganization energy of 0.4 eV (λin). A stopped-flow kinetic study results reveal an outer-sphere electron transfer process with a total reorganization energy (λ) of 1.1 eV between 2(1,2) and 3 calculated in the context of Marcus theory.
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