ArticleJournal of the American Chemical Society2016
Perturbing the Copper(III)-Hydroxide Unit through Ligand Structural Variation.
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 62 papers.
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Who cites it
62 citing papers in PubMed, 131 citations in OpenAlex.
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- Lewis acidity of a high-valent copper(iii) acetylacetonate.RSC advances · 2026Article
- Hydroquinone Oxidation by Redox-active Guanidines and Thioguanidines: Faster Conversion to High-Potential Than to Low-Potential Quinones.Chemistry (Weinheim an der Bergstrasse, Germany) · 2026Article
- High-Valent Late Transition Metal-Oxo Complexes: Breaking Boundaries at the Oxo Wall and Beyond.Chemical reviews · 2026Review
- Concerted Proton-Electron Transfer Minimizes Substituent Effects on Adsorbed Phthalocyanine Electrocatalysis.Journal of the American Chemical Society · 2026Article
- Unprecedented Formation of a Formally Cu(III) Trifluoromethyl Hydroxide Tetramer.Chemistry (Weinheim an der Bergstrasse, Germany) · 2026Article
- Distinct hydrogen atom transfer and radical capture reactivity of copper(iii) OH/F complexes enables site-selective C(spChemical science · 2026Article
- Hydrogen Atom Abstraction via Hydride-Coupled Electron Transfer and Its Origin.Inorganic chemistry · 2025Article
- Stepwise 6HInorganic chemistry · 2025Article
- C(spJournal of the American Chemical Society · 2025Article
- High-Valent Intermediate Observed in a Cu-Based OER Electrocatalyst byThe journal of physical chemistry letters · 2025Article
- The Role of Electron Transfer in Copper-Mediated C(spAngewandte Chemie (International ed. in English) · 2025Article
- From [2Mn2S] Diamond Cores to Butterfly Rhombs: Transformations That Highlight Alternating Peptide Binding Sites.Inorganic chemistry · 2024Article
- High pressure-derived nonsymmetrical [CuScience advances · 2024Article
- Unraveling the Mechanism of Hydrogen Atom Transfer by a Nickel-Hypochlorite Species and the Influence of Electronic Effects.Inorganic chemistry · 2024Article
- Identifying Radical Pathways for Cu(I)/Cu(II) Relay Catalyzed Oxygenation via Online Coupled EPR/UV-Vis/Near-IR Monitoring.Advanced science (Weinheim, Baden-Wurttemberg, Germany) · 2024Article
- Copper-oxygen adducts: new trends in characterization and properties towards C-H activation.Chemical science · 2024Review
- Tuning the Thermochemistry and Reactivity of a Series of Cu-Based 4HInorganic chemistry · 2024Article
- 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
2 more citing papers are in PubMed but not listed here.
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Authors and funding
8 authors at 1 institution in 1 country.
Funding
Abstract
Two new ligand sets, (pipMe)LH2 and (NO2)LH2 ((pipMe)L = N,N'-bis(2,6-diisopropylphenyl)-1-methylpiperidine-2,6-dicarboxamide, (NO2)L = N,N'-bis(2,6-diisopropyl-4-nitrophenyl)pyridine-2,6-dicarboxamide), are reported which are designed to perturb the overall electronics of the copper(III)-hydroxide core and the resulting effects on the thermodynamics and kinetics of its hydrogen-atom abstraction (HAT) reactions. Bond dissociation energies (BDEs) for the O-H bonds of the corresponding Cu(II)-OH2 complexes were measured that reveal that changes in the redox potential for the Cu(III)/Cu(II) couple are only partially offset by opposite changes in the pKa, leading to modest differences in BDE among the three compounds. The effects of these changes were further probed by evaluating the rates of HAT by the corresponding Cu(III)-hydroxide complexes from substrates with C-H bonds of variable strength. These studies revealed an overarching linear trend in the relationship between the log k (where k is the second-order rate constant) and the ΔH of reaction. Additional subtleties in measured rates arise, however, that are associated with variations in hydrogen-atom abstraction barrier heights and tunneling efficiencies over the temperature range from -80 to -20 °C, as inferred from measured kinetic isotope effects and corresponding electronic-structure-based transition-state theory calculations.
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Registered trials
Read under generation 80e0d062 · epoch 390. Bibliography from PubMed, PubMed Central and OpenAlex; grants from NIH RePORTER; trial links from ClinicalTrials.gov; estimates, votes and beliefs from the OpenQuestion graph.