Catalytic Aerobic Oxidation of Alcohols by Copper Complexes Bearing Redox-Active Ligands with Tunable H-Bonding Groups.

In this research article, we describe the structure, spectroscopy, and reactivity of a family of copper complexes bearing bidentate redox-active ligands that contain H-bonding donor groups. Single-crystal X-ray crystallography shows that these tetracoordinate complexes are stabilized by intramolecular H-bonding interactions between the two ligand scaffolds. Interestingly, the Cu complexes undergo multiple reversible oxidation-reduction processes associated with the metal ion (CuI, CuII, CuIII) and/or the o-phenyldiamido ligand (L2-, L•-, L). Moreover, some of the CuII complexes catalyze the aerobic oxidation of alcohols to aldehydes (or ketones) at room temperature. Our extensive mechanistic analysis suggests that the dehydrogenation of alcohols occurs via an unusual reaction pathway for galactose oxidase model systems, in which O2 reduction occurs concurrently with substrate oxidation.

• Publication year

  2018

• Venue

  Journal of the American Chemical Society

• Publication date

  2018-11-06

• Fields of study

  Medicine, Chemistry

• Identifiers
  DOI 10.1021/jacs.8b08748PMID 30400740PMCID PMC6645702
• External record

  Open on Semantic Scholar

• Source metadata

  Semantic Scholar, PubMed

• No claims are published for this paper.

• No concepts are published for this paper.

• Intramolecular Hydrogen Bonding Enhances Stability and Reactivity of Mononuclear Cupric Superoxide Complexes.

  2018cited by this paper
• Hydrogen Bonds Dictate O2 Capture and Release within a Zinc Tripod.

  2018cited by this paper
• Electronic Structural Analysis of Copper(II)-TEMPO/ABNO Complexes Provides Evidence for Copper(I)-Oxoammonium Character.

  2017cited by this paper
• Reactivity of an FeIV-Oxo Complex with Protons and Oxidants.

  2016cited by this paper
• New avenues for ligand-mediated processes--expanding metal reactivity by the use of redox-active catechol, o-aminophenol and o-phenylenediamine ligands.

  2015cited by this paper
• Molecular designs for controlling the local environments around metal ions.

  2015cited by this paper
• Redox Non-innocent Ligand Controls Water Oxidation Overpotential in a New Family of Mononuclear Cu-Based Efficient Catalysts.

  2015cited by this paper
• Lewis acid-induced change from four- to two-electron reduction of dioxygen catalyzed by copper complexes using scandium triflate.

  2015cited by this paper
• Copper active sites in biology.

  2014cited by this paper
• (Electro)catalytic C-C bond formation reaction with a redox-active cobalt complex.

  2014cited by this paper
• Mechanism of alcohol oxidation mediated by copper(II) and nitroxyl radicals.

  2014cited by this paper
• Mechanism of copper(I)/TEMPO-catalyzed aerobic alcohol oxidation.

  2013cited by this paper
• Redox-active ligands in catalysis.

  2013cited by this paper
• Copper/TEMPO-Catalyzed Aerobic Alcohol Oxidation: Mechanistic Assessment of Different Catalyst Systems.

  2013cited by this paper
• Nonprecious-metal-assisted photochemical hydrogen production from ortho-phenylenediamine.

  2013cited by this paper
• Redox Non-Innocent Ligands: Versatile New Tools to Control Catalytic Reactions

  2012cited by this paper
• Role of metal-oxo complexes in the cleavage of C-H bonds.

  2011cited by this paper
• Manifestations of noninnocent ligand behavior.

  2011cited by this paper
• Cytochrome P450 Compound I: Capture, Characterization, and C-H Bond Activation Kinetics

  2010cited by this paper
• O2 activation and selective phenolate ortho hydroxylation by an unsymmetric dicopper mu-eta1:eta1-peroxido complex.

  2010cited by this paper
• Mononuclear copper complex-catalyzed four-electron reduction of oxygen.

  2010cited by this paper
• P450 enzymes: their structure, reactivity, and selectivity-modeled by QM/MM calculations.

  2010cited by this paper
• Radical Ligands Confer Nobility on Base-Metal Catalysts

  2010cited by this paper
• A series of metal complexes with the non-innocent N,N'-bis(pentafluorophenyl)-o-phenylenediamido ligand: twisted geometry for tuning the electronic structure.

  2008cited by this paper
• The combination of transition metal ions and hydrogen-bonding interactions.

  2008cited by this paper
• Joint spectroscopic and theoretical investigations of transition metal complexes involving non-innocent ligands.

  2007cited by this paper
• Bioinspired hydrogen bond motifs in ligand design: the role of noncovalent interactions in metal ion mediated activation of dioxygen.

  2005cited by this paper
• Three-spin system with a twist: a bis(semiquinonato)copper complex with a nonplanar configuration at the copper(II) center.

  2005cited by this paper
• Dioxygen activation at mononuclear nonheme iron active sites: enzymes, models, and intermediates.

  2004cited by this paper
• Free radical catalysis by galactose oxidase.

  2003cited by this paper
• The hydrogen bond in the solid state.

  2002cited by this paper
• Electronic structure of bis(o-iminobenzosemiquinonato)metal complexes (Cu, Ni, Pd). The art of establishing physical oxidation states in transition-metal complexes containing radical ligands.

  2001cited by this paper
• Kinetic isotope effects as probes of the mechanism of galactose oxidase.

  1998cited by this paper
• Catalytic galactose oxidase models: biomimetic Cu(II)-phenoxyl-radical reactivity.

  1998cited by this paper
• Hydrogen Bonding in Organometallic Crystals. 6.† X−H---M Hydrogen Bonds and M---(H−X) Pseudo-Agostic Bonds

  1997cited by this paper
• Copper-Catalyzed Oxidation of Alcohols to Aldehydes and Ketones: An Efficient, Aerobic Alternative

  1996cited by this paper
• Galactose Oxidase Model Complexes: Catalytic Reactivities

  1996cited by this paper
• Hydrogen bonding in nucleosides and nucleotides

  1985cited by this paper

• Ligand design and catalytic performance of Quinone-oxime copper complexes: role of intramolecular hydrogen bonding

  2026cites this paper
• Surface immobilization of TiO2@Fe3O4 nanoparticles by diimine-chelate of cis-Mo(VI)O2-ion catalyst for development and sustainability of the esterification reactions of alkenes

  2026cites this paper
• Synthesis, Crystallographic Study and Antibacterial Activity of Ternary Copper(II) Complex with Chromone-Based Ligand and Pyridine

  2025cites this paper
• Chromium and Manganese Complexes of Pincer‐Like Azo‐Amine Ligands: Synthesis, Characterization, and their Catalytic CC Bond Formation Reaction with Fluorenes and Alcohols

  2025cites this paper
• Sustainable Multicomponent Synthesis of Benzoxazoles from Alcohols and Aldehydes Catalyzed by Copper Catalysts

  2025cites this paper
• Reduction of Nitrite at a Copper(II) Trans-κ1-ONO Complex via Proton-Coupled Electron Transfer and Oxygen Atom Transfer.

  2025cites this paper
• Complexation Features of Quinoxalyl‐Hydrazone Ligand Towards Oxo‐Zirconium (IV) and Oxo‐Vanadium (IV) Ions for Biological Studies and Catalytic Oxidation of Alcohols

  2025cites this paper
• Variation of the Redox Properties and Coordination Chemistry of Redox‐Active Aromatic Diguanidine Ligands with the Substitution Pattern

  2025cites this paper
• Supported Copper(II) Arylhydrazone Complex on Synthesized Fe3O4 Nanoparticles Boosted with TiO2 for the Catalytic Oxidation of Alcohols.

  2025cites this paper
• Immobilized Copper(II) Diisatin-Schiff Base Complex on AgCo3O4 Nanoparticles as Efficient Catalysts for Styrene Oxidation.

  2025cites this paper
• Aerial Oxidation of Alcohols by an Amide and Imidazole Functionalized Bioinspired Cu‐Complex and Its Switching with N‐Oxides

  2025cites this paper
• Tuning Reactivity in Cu/TEMPO Catalyzed Alcohol Oxidation Reactions

  2025cites this paper
• An o-Phenylene Bridged Noninnocent Bis-Azopyridyl Ligand and Its Copper Complexes: Synthesis, Characterization of Electron Transfer Events, and Use of the Cu Complexes for Oxidation of Alcohols.

  2025cites this paper
• Synthetic and characteristic strategies of FeII and VIVO-complexation from Schiff base diol chelating ligand for catalytic 1,2-cyclooctene epoxidation and biological studies

  2025cites this paper
• Structural influence of new fabricated CoII and CuII-diol Schiff-base complexes on catalytic epoxidizing reactions and biological efficacy

  2025cites this paper
• Cobalt(II) complexes of tri-dentate S,N,S-thiophenyl Schiff base ligand for prospective biological studies and ct-DNA interaction. Catalytic benzyl alcohol oxidative performance

  2025cites this paper
• Advancing Propylene Epoxidation: The Role of Ethyl Acetate Autoxidation via Cobalt-Nickel Catalyzed C(acyl)-O Bond Scission.

  2025cites this paper
• Biological and Catalytic Evaluation for Nickel (II) and Oxyvanadium (II) Chelates of tri‐Dentate Hydrazone‐Quinoxalyl Ligand

  2025cites this paper
• Manganese(II) complexes of thiophenyl imino-ligand with synergistic behavior in biological systems, ct-DNA interactions, and catalytic oxidative performance of benzyl alcohol

  2025cites this paper
• Synergistic effect of copper(II) di-iminophenol complex catalyst immobilized on Fe3O4-TiO2 nanocomposite: Homogeneity and heterogeneity in organic thiophene oxidation

  2025cites this paper
• Recent advances in metal-catalysed oxidation reactions

  2025cites this paper
• A Terminal Germanium Oxido Dianion by Structural Constraints.

  2025cites this paper
• Electrocatalytic Semihydrogenation of Terminal Alkynes Using Ligand-Based Transfer of Protons and Electrons.

  2024cites this paper
• Exploring Cu(II) and Zn(II) complexes of 1,4-naphthoquinoneoxime as bioinspired catalysts for alcohol oxidation

  2024cites this paper
• Cu-ABNO Catalyst for the Synthesis of Quinolines and Pyrazines via Aerobic Double Dehydrogenation of Alcohols.

  2024cites this paper
• NHPI-Catalyzed Electro-Oxidation of Alcohols to Aldehydes and Ketones.

  2024cites this paper
• Leveraging ligand-based proton and electron transfer for aerobic reactivity and catalysis

  2024cites this paper
• Immobilized transition metal (II) bis–imine chelate on ZnO@TiO2 nanoparticles as sufficient catalysts for alcohol oxidation and for α,β‐cinnamic acid decarboxylative bromination

  2024cites this paper
• Copper(I) complexes of 1,2-bis(diphenylphosphino)benzene as efficient catalysts for alkyne hydroamination and azide-alkyne cycloaddition

  2024cites this paper
• Copper on charcoal: TEMPO free Cu0 nanoparticles catalyzed aerobic oxidation of alcohols

  2023cites this paper
• Photochemical Oxidation of Alcohols to Ketones or Aldehydes Using Dmso as an Oxidant Without Activated Agent

  2023cites this paper
• Transition metal oxide complexes as molecular catalysts for selective methane to methanol transformation: any prospects or time to retire?

  2023cites this paper
• Quantitative Electromerism of a Well-defined Mononuclear Copper Complex Through Reversible Intramolecular Metal-Ligand Electron Transfer.

  2023cites this paper
• Imaging the Dynamics of Metal Ion-Coupled Electron Transfer on Material Surfaces with Redox/Photo Active Chelators.

  2023cites this paper
• ZnO–TiO2 Nanoparticles Coated by the Dioxomolybdenum (VI) bis-Schiff Base Complex for Catalytic Oxidation of Sulfides

  2023cites this paper
• Facile synthetic route of TiO2-ZnO heteronanostructure coated by oxovanadium (IV) bis-Schiff base complex as a potential effective homogeneous/heterogeneous catalysts for alcohols redox systems

  2023cites this paper
• Two-Electron Redox Tuning of Cyclopentadienyl Cobalt Complexes Enabled by the Phenylenediamide Ligand.

  2023cites this paper
• Carboxamide Fe(III) complex as the electrocatalyst of water oxidation reaction: WNA and I2M O–O bond formation pathways

  2023cites this paper
• Geometric Control of Cu, Ni and Pd Complexes in the Solid State via Intramolecular H-Bonding Interactions

  2023cites this paper
• Novel bioinspired dinuclear Cu(II) ‘paddle wheel’ acetate complex: catalytic and in vitro biological activity studies

  2023cites this paper
• Molecular Mechanism of the Mononuclear Copper Complex Catalyzed Water Oxidation from Cluster-Continuum model calculations.

  2022cites this paper
• Photoactivation of titanium-oxo cluster [Ti6O6(OR)6(O2CtBu)6]: mechanism, photoactivated structures, and onward reactivity with O2 to a peroxide complex

  2022cites this paper
• Copper Based Biomimetic Catalysts of Catechol Oxidase: An Overview on Recent Trends

  2022cites this paper
• Hemilabile Amine-Functionalized Efficient Azo-Aromatic Cu-Catalysts Inspired by Galactose Oxidase: Impact of Amine Sidearm on Catalytic Aerobic Oxidation of Alcohols.

  2022cites this paper
• Ligand-Based Redox: Catalytic Applications and Mechanistic Aspects

  2022cites this paper
• Redox-active ligands for chemical, electrochemical, and photochemical molecular conversions

  2022cites this paper
• A 4H+/4e- Electron-Coupled-Proton Buffer Based on a Mononuclear Cu Complex.

  2022cites this paper
• Biomimetic catalytic aerobic oxidation of C–sp(3)–H bonds under mild conditions using galactose oxidase model compound CuIIL

  2022cites this paper
• Rapid Catalysis for Aerobic Oxidation of Alcohols Based on Nitroxyl-Radical-Free Copper(II) under Ambient Conditions

  2022cites this paper
• Generation and Aerobic Oxidative Catalysis of a Cu(II) Superoxo Complex Supported by a Redox-Active Ligand.

  2022cites this paper
• Cobalt-Catalyzed Hydrogenation Reactions Enabled by Ligand-Based Storage of Dihydrogen

  2022cites this paper
• Exploring the Reaction Mechanism of C-H Oxidation by Copper-Salen Complexes.

  2022cites this paper
• Exovinylene Cyclic Carbonates: Multifaceted CO2-Based Building Blocks for Modern Chemistry and Polymer Science.

  2022cites this paper
• Theoretical perspective on mononuclear copper-oxygen mediated C–H and O–H activations: A comparison between biological and synthetic systems

  2022cites this paper
• Synthesis of heteroleptic phosphine–copper(i) complexes: fluorescence sensing and catalytic properties

  2021cites this paper
• Novel Oxidovanadium Complexes with Redox-Active R-Mian and R-Bian Ligands: Synthesis, Structure, Redox and Catalytic Properties

  2021cites this paper
• Copper Complexes of the Tetradentate N,N′ ‐Bis(2‐amino‐3,5‐di‐ tert ‐butylphenyl)‐2,2′‐diaminobiphenyl Ligand

  2021cites this paper
• Highly efficient oxidation of alcohols catalyzed by Ru(II) carbonyl complexes bearing salicylaldiminato ligands

  2020cites this paper
• Zn-doped W/aluminium oxide catalyst: Efficient strategy towards sustainable oxidation of alcohols

  2020cites this paper
• Spin-resolved charge displacement analysis as an intuitive tool for the evaluation of cPCET and HAT scenarios.

  2020cites this paper
• Cu-Mn Bimetallic Complex Immobilized on Magnetic NPs as an Efficient Catalyst for Domino One-Pot Preparation of Benzimidazole and Biginelli Reactions from Alcohols

  2020cites this paper
• Dioxygen Activation by Internally Aromatic Metallacycle: Crystallographic Structure and Mechanistic Investigations

  2020cites this paper
• Structure, spectroscopy and reactivity of a mononuclear copper hydroxide complex in three molecular oxidation states.

  2020cites this paper
• Generation and Oxidative Reactivity of a Ni(II) Superoxo Complex via Ligand-Based Redox Non-Innocence.

  2020cites this paper
• Bond Activations Assisted by Redox Active Ligand Scaffolds

  2020cites this paper
• Copper catalysis with redox-active ligands

  2020cites this paper
• Tuning of the redox potential and catalytic activity of a new Cu(ii) complex byo-iminobenzosemiquinone as an electron-reservoir ligand

  2020cites this paper
• Cyclohexene Promoted Efficient Biomimetic Oxidation of Alcohols to Carbonyl Compounds Catalyzed by Manganese Porphyrin under Mild Conditions

  2020cites this paper
• Design and synthesis of a versatile cooperative catalytic aerobic oxidation system with co-immobilization of palladium nanoparticles and laccase into the cavities of MCF

  2020cites this paper
• Synthesis, characterization and antimicrobial properties of mononuclear copper(II) compounds of N,N′-di(quinolin-8-yl)cyclohexane-1,2-diamine

  2019cites this paper
• Tris(pyrazolyl)borate Copper Hydroxide Complexes Featuring Tunable Intramolecular H-Bonding.

  2019cites this paper
• Formation of the Cu(II)-phenoxyl radical by reaction of O₂ with the Cu(II)-phenolate complex via the Cu(I)-phenoxyl radical.

  2019cites this paper
• Nickel complexes of ligands derived from (o-hydroxyphenyl) dichalcogenide: delocalised redox states of nickel and o-chalcogenophenolate ligands.

  2019cites this paper
• Inter-ligand delocalisations in transition metal complexes containing multiple non-innocent ligands.

  2019cites this paper
• Enhancing the Regioselectivity of B(C6F5)3-Catalyzed Epoxide Alcoholysis Reactions Using Hydrogen-Bond Acceptors

  2019cites this paper
• Carboxamidate Ligand Noninnocence in Proton Coupled Electron Transfer.

  2019cites this paper
• Tunable intramolecular multicenter H-bonding interactions in first-row metal complexes bearing bidentate redox-active ligands

  2019cites this paper