Catalytic Oxidation Reactions Research Articles

Manganese Catalyzed Partial Oxidation of Light Alkanes

The catalytic partial oxidation of methane is achieved at low temperatures (<200 °C) using manganese oxides and manganese salts in mixtures of trifluoroacetic acid and trifluoroacetic anhydride. Dioxygen is used as the in situ terminal oxidant. For Mn oxides (e.g., MnO2, Mn2O3, and Mn3O4), we studied stoichiometric methane partial oxidation in HTFA (TFA = trifluoroacetate). Using a Mn trifluoroacetate salt, at 180 °C and under 25 psig of methane, product selectivity for the mono-oxidized product methyl trifluoroacetate (MeTFA) is observed to be >90% at ∼35% methane conversion at approximately 6 turnovers. Under our catalytic methane oxidation reaction conditions, MeTFA is stable against overoxidation, which explains the likely high selectivity at conversions >15%. Using combined experimental studies and DFT calculations, a mechanism involving soluble and molecular Mn species in the catalytic cycle is proposed. The proposed reaction pathway involves initial activation of MnII by dioxygen, cleavage of a methane C–H bond by a MnIII hydroxo intermediate, rebound of the methyl radical to generate MeTFA, and finally regeneration of the starting MnII complex. Also, this process is shown to be applicable to the oxidation of ethane, favoring the mono-oxidized product ethyl trifluoroacetate (EtTFA) and reaching ∼46% conversion.

Guiding questions for the synthesis of catalyst and its application in selective catalytic oxidation reactions

This paper presents a brief history of catalysis, as well as the processes of selective oxidation of hydrocarbons. On the other hand, the basic concepts involved in heterogeneous catalysis are mentioned, emphasizing the role of catalytic materials in chemical oxidation processes and posing a series of guiding questions to be followed when approaching a process catalyzed by solid materials. In the same way, the methods of synthesis of catalysts known in the literature as sol-gel and impregnation are shown, identifying the influence of each stage of preparation with the physical and chemical properties of the materials. Finally, a case study applied to the selective catalytic oxidation of methane and methanol using iron, molybdenum, and vanadium catalytic materials synthesized by the sol-gel method is presented.

Aerobic Oxidation Reactivity of Well-Defined Cobalt(II) and Cobalt(III) Aminophenol Complexes.

This paper describes the synthesis and reactivity studies of three cobalt complexes bearing aminophenol-derived ligands without nitrogen substitution: CoII(tBu2APH)2(tBu2AP)2 (1), CoIII2(tBu2APH)2(tBu2AP)2(μ-tBu2BAP)2 (2), and CoIII(tBu2AP)3 (3), where tBu2APH = 2-amino-4,6-di-tert-butylphenol, tBu2AP = 2-amino-4,6-di-tert-butylphenolate, and μ-tBu2BAP = bridging 2-amido-4,6-di-tert-butylphenolate. Stoichiometric reactivity studies of these well-defined complexes demonstrate the catalytic competency of both cobalt(II) and cobalt(III) complexes in the aerobic oxidative cyclization of tBu2APH with tert-butylisonitrile. Reactions with O2 reveal the aerobic oxidation of the cobalt(II) complex 1 to generate the cobalt(III) species 2 and 3. UV-visible time-course studies and electron paramagnetic resonance spectroscopy indicate that this oxidation proceeds through a ligand-based radical intermediate. These studies represent the first example of well-defined cobalt aminophenol complexes that participate in catalytic aerobic oxidation reactions and highlight a key role for a ligand radical in the oxidation sequence.

Methane Monooxygenase Mimic Asymmetric Oxidation: Self-Assembling μ-Hydroxo, Carboxylate-Bridged Diiron(III)-Catalyzed Enantioselective Dehydrogenation.

Mimicking naturally occurring metalloenzymes to enrich the diversity of catalytic asymmetric oxidation reactions is a long-standing goal for modern chemistry. Toward this end, a range of methane monooxygenase (MMO) mimic chiral carboxylate-bridged (μ-hydroxo) diiron(III) dimer complexes using salan as basal ligand and sodium aryl carboxylate as additive have been designed and synthesized. The chiral diiron complexes exhibit efficient catalytic reactivity in dehydrogenative kinetic resolution of indolines using environmentally benign hydrogen peroxide as oxidant. In particular, complex C9 bearing sterically encumbered salan ligands and a 2-naphthoate bridge is identified as the optimal catalyst in terms of chiral recognition. Further investigation reveals that this MMO mimic chiral catalyst can be readily generated by self-assembly under the dehydrogenation conditions. The self-assembling catalytic system is applicable to a series of indolines with multiple stereocenters and diverse substituent patterns in high efficiency with a high level of chiral recognition (selectivity factor up to 153). Late-stage dehydrogenative kinetic resolution of bioactive molecules is further examined.

3D hierarchical local heterojunction as ultra-highly efficient Fenton-like catalyst: Mechanism of coupling the proton-coupled electron transfer under nanoconfinement effect

Charge transfer in general type-II heterojunction is hard to realize and the transfer mode weakens the overall redox ability of the heterojunction. Band regulation and surface interface structural modifications assembled a novel visible-light-driven homogeneous catalyst (FeS2 anchored on Mo2C aerogel), which activated the peroxymonosulfate (PMS) by proton-coupled electron transfer effect under the nanoconfinement effect.The degradation rate constant of the FeS2@Mo2C/PMS system is 11.4 times that of the PMS system and 2.6 times that of the Fe(Ⅱ) + Mo2C + PMS Fenton-like system. The initial pH has almost no effect on the degradation rate of the FeS2@Mo2C/PMS system. The EPR results show that the FeS2@Mo2C heterostructure can effectively catalyze the production of SO4·−, HO· and 1O2 by PMS, which is in agreement with the quenching results. DFT calculations demonstrate the existence of stable SMo bonds in FeS2@Mo2C Schottky junctions. Thus S vacancies in FeS2 significantly accelerated the transfer of FeS2 photogenerated electrons to Mo2C, FeS2 photogenerated holes can directly oxidize Azo dyes, extensively promoting the catalytic oxidation reaction rate. The prepared mesoporous catalysts (average pore diameter = 58.13 nm) through nanoconfinement effect can effectively accelerate the transmission speed to achieve the target pollutants > 99.9% removal rate in five min under sufficient catalyst. This paper provides a new perspective on applying Schottky heterojunctions coupled with photocatalytic technology for the effective degradation of Azo dyes.

Oxidative desulfurization of a model fuel using MoO3 nanoparticles supported on carbon nanotubes catalyst: Examine most significance variables, optimization, kinetics and thermodynamics study

Molybdenum oxide nanoparticles MONP were dispersed on multiwall nanotubes MWNTs as an attempt to synthesize MONP/MWNTs catalyst, the synthesis method done by wet impregnation. The prepared catalyst was characterized by FTIR (Fourier –Transform Infrared Spectroscopy) and, XRD (X-ray diffraction), whilst the catalyst activity is done with catalytic oxidative desulfurization ODS reaction for oxidation dibenzothiophene DBT dissolved in heptane (model fuel) with hydrogen peroxide H2O2, in which catalyst activity investigation achieved via studying impact six from most affected variables on ODS reaction. The chosen variables are reaction temperature, contact time, sulfur initial sulfur concentration, stirring speed, oxidant/sulfur ratio and catalyst dosage, and then the studied variables were screened by application of Plackett-Burman design PBD to identify the more significant on response (DBT pollutant removal). DBT pollutant removal is referred to as sulfur removal efficiency. Analysis of variance ANOVA shows that the reaction temperature, oxidant/sulfur ratio, stirring speed, and sulfur initial concentration are the most significant from the chosen variables due to their F-values 37.60, 25.45, 11.62 and 6.71 respectively. Box –Behnken experimental design was used to complete the study the effect of the most significant more deeply on ODS reaction (sulfur removal efficiency),in which this part exhibited that sulfur removal efficiency at range between 51 and 93%, whilst the optimum sulfur removal efficiency was 96% at 70 °C,4.36, 957 rpm and 50 ppm for reaction temperature, oxidant/sulfur ration, stirring speed and initial sulfur concentration respectively. The study involves estimation of kinetics and thermodynamics parameters for ODS reaction; kinetics studying exhibited that ODS reaction followed pseudo-first-order reaction with activation energy (12.996 kJ/mol), while the thermodynamics study shows the low negative entropy change (-0.221 kJ /mol.K), positive enthalpy and free energy changes which confirm a high hydrate transition complex was formed.

Optimizing treatment of alcohol vinasse using a combination of advanced oxidation with porous α-Fe2O3 nanoparticles and coagulation-flocculation

This study utilizes a novel method, namely the combination of advanced oxidation processes with synthesized highly porous α-Fe2O3 nanoparticles and coagulation-flocculation with polyacrylamide, to investigate the effects on COD removal in alcohol vinasse. Highly porous α-Fe2O3 nanoparticles were prepared via a chemical precipitation technique. The characteristic of the synthesized α-Fe2O3 nanoparticles were determined by FT-IR, Raman spectroscopy, XRD, SEM, and N2 adsorption-desorption isotherms. The effect of different α-Fe2O3 nanoparticles loading for chemical oxygen demand (COD) removal efficiency was investigated. The results revealed that at α-Fe2O3 nanoparticle dose of 3000 ppm had the highest COD removal for vinasse. Then, central composite design (CCD) was used to optimize the operating variables such as pH, time, oxidant dosage, and coagulant dosage, and their optimum values were determined to be pH:7.36, 90 min, 17.89 wt% oxidant dosage, and 1.6 wt% coagulant dosage, to achieve a high COD removal efficiency in 70 ℃ for alcohol vinasse (98.64%). Based on optimal conditions, the porous α-Fe2O3 nanoparticles possess superior catalytic activity in the advanced oxidation process compared to other treating methods. Also, the mechanism of the catalytic oxidation reaction is evaluated.

Catalytic Magnesium-Oppenauer Oxidation of Alcohols

Abstract A catalytic magnesium-Oppenauer oxidation reaction was developed. When a solution of alcohols in toluene was successively treated with 15–30 mol % of EtMgBr and 1.0 equiv. of trifluoromethyl ketone (oxidant), a hydride transfer-type oxidation reaction (Oppenauer oxidation) occurred to give corresponding ketones in good chemical yields (up to 85%). It was noteworthy that even a weakly basic alkoxide derived from trifluoromethyl ketone worked as an efficient Brønsted base to deprotonate the starting material (alcohols) at ambient temperature (25 °C). The efficiency of the present method was highlighted by applying the method to substrates having a nitrogen atom, which were sensitive to various oxidation conditions.

Highly efficient NHC‐iridium(I) catalyzed disulfide bond forming reaction

The N‐heterocyclic carbene (NHC) iridium(I) complex [IrCl (COD)(IMes)] [IMes = 1,3‐bis(2,4,6‐trimethylphenyl) imidazole‐2‐ylidene] showed an excellent catalytic activity in the reactions of the aerobic oxidative coupling of thiols into disulfides. The use of oxygen of air as a green oxidant allows the thiols to be quantitatively converted into the corresponding disulfides under mild conditions and in a short reaction time. The replacement of chloride ligand on the iridium by the strong‐donating thiolate ligand yielded an electron‐rich and sensitive‐to‐oxygen active species [Ir(S‐R)(COD)(IMes)] at room light and subsequently promoting the catalytic oxidative coupling reactions. This active species was successfully isolated and characterized by X‐ray diffraction and found also to be essential in revealing a plausible mechanism for this Ir‐catalyzed transformation. The Density Functional Theory (DFT)‐calculated free energy profile of the proposed mechanism of our developed catalyst system can reasonably account for the key role of air in pursuing the catalytic reaction. Overall, the obtained computational and the experimental results of this study are in good agreement.

Adsorption and dissociation mechanism of toluene on Pd (111) and PdO (101) surface: First principle calculation

Metal Palladium species are efficiently used to degrade volatile organic compounds (VOCs). In this paper, the adsorption properties of toluene on Pd(111) and PdO(101) surfaces were theoretically studied using the first principle calculation. Adsorption energy, charge density, density of states and electron density difference were chosen as characteristics and were calculated to evaluate the adsorption capacity of toluene on Pd(111) and PdO(101) surfaces. The results showed that the interaction of toluene on the Pd(111) surface was stronger than on the PdO(101) surface. The dissociation pathway of toluene after adsorption was also determined; the results showed that the formation of benzyl radical through the reaction with a hydroxyl group on the Pd(111) and PdO(101) surfaces was investigated using density functional theory calculations. Compared with PdO(101) (0.63 eV), the dissociation of toluene on Pd(111) (0.19 eV) has a lower energy barrier, which indicated that the reaction between toluene and Pd(111) was easier to occur. Therefore, it provides the basis for the preparation of high-performance catalysts and the calculation of catalytic oxidation reaction paths in the future.

From Biomass to the KarrikinsviaSelective Catalytic Oxidation of Hemicellulose‐Derived Butyl Xylosides and Glucosides

AbstractMembers of the karrikin family of bioactive small molecules are known to promote germination of a range of plants following large scale fires. As a result, they are relevant and interesting compounds. This report describes their synthesis from a biomass‐derived product stream. During work to fractionate biomass with the goal of obtaining high quality lignins, an interesting co‐product stream derived from the hemicellulose in the biomass, was obtained. Whilst many applications of this co‐product stream can be proposed, in this case the major monosaccharides have been converted to relevant karrikins in short reaction sequences. Key results include a highly selective catalytic oxidation reaction, conversion of the resulting ketone to a butenolide by two alternative approaches, a selective acetal reductive opening reaction, X‐ray crystallographic analysis of two compounds and detailed comparison of the final products with previous literature reports. Only through successful use of all the components generated during biomass refining, can economic sustainability be potentially achieved.

Decontamination of arsenite by a nano-sized lanthanum peroxide composite through a simultaneous treatment process combined with spontaneously catalytic oxidation and adsorption reactions

Arsenic is a well-documented element that is extremely harmful to humans. Among major arsenic species in nature, arsenite (As(III)) has higher mobility and toxicity, and is more difficult to be treated by such technologies as coagulation or adsorption than arsenate (As(V)). As such, its decontamination is greatly challenging. Herein, a new nano-sized lanthanum peroxide composite (LPC) with H2O2-to-La3+ molar ratio of 1:1 developed through a simple precipitation method can simultaneously oxidize and adsorb arsenite. The LPC exhibited rapid arsenite oxidation and adsorption kinetics in pH 4.5–10.8 and the uptake was completed at time = 60 min; it had a strong selectivity in the presence of competing matters. Moreover, the LPC had a superior As(III) adsorption capacity of 123.2 mg-As/g, outperforming many reported adsorbents. Both As(III) and As(V) in simulated arsenic-polluted reservoir waters were rapidly removed and the rigorous arsenic standard of 10 μg/L was met. Our mechanism studies showed that the oxidation of arsenite to arsenate was ascribed to the La-O-O- groups and the derived OH generated through the self-catalytic process via the electron transfer within internal peroxo groups. The formed arsenate was bonded to the LPC surface, forming stable inner-sphere complexes via electrostatic attraction and ligand exchange with surface hydroxyls. The study reported here demonstrates that the LPC is promising for the simultaneous oxidation and removal of arsenite from aqueous solutions.

Fluorophore-mediated Photooxidation of the Guanine Heterocycle.

Fluorescent dyes are routinely used to visualize DNA or RNA in various experiments, and some dyes also act as photosensitizers capable of catalyzing oxidation reactions. The present studies explored whether the common labeling dyes fluorescein, rhodamine, BODIPY, or cyanine3 (Cy3) can function as photosensitizers to oxidize nucleic acid polymers. Photoirradiation of each dye in the presence of the guanine (G) heterocycle, which is the most sensitive toward oxidation, identified slow rates of nucleobase oxidation in the nucleoside and DNA contexts. For all four fluorophores studied, the only product detected was spiroiminodihydantoin (Sp) suggesting the dyes functioned as Type II photosensitizers and generate singlet oxygen (1O2). The nucleoside reactions were then conducted in D2O solutions, known to increase the lifetime of 1O2, which resulted in a ~6-fold increase in the Sp yield, further supporting the classification of these dyes as Type II photosensitizers. Lastly, we inspected the pattern of G reactivity with the dyes upon photoirradiation in the context of a parallel-stranded G-quadruplex. The G nucleotides in the two exterior G-tetrads were found to be oxidation prone, providing the third line of evidence that the dyes are Type II photooxidants. The present work found that the common dyes fluorescein, rhodamine, BODIPY, or Cy3 can drive G oxidation but with a slow rate and low overall yield. This will likely not impact many experiments using dyes to study nucleic acids except for those that have long exposures with high-intensity lights, such as sequencing-by-synthesis experiments using fluorescence as the readout.

Molecular traffic control for catalytic oxidation reaction in TS-1 zeolite

For four decades, the definition of “molecular traffic control (MTC effect)” in zeolite shape selective catalysis has been controversially discussed. So far, there is no clear evidence to prove the existence of MTC effect in the catalytic oxidation reaction. In this work, a series of TS-1 zeolites with homogeneous distribution of Ti atoms and free of extra-framework Ti species and/or anatase were synthesized, they were used to catalyze the oxidation of 1-hexene, 4-methyl-1-pentene and styrene. The systematic investigations exhibited that the catalytic oxidation process of TS-1/H 2 O 2 occurred in both straight and sinusoidal channels when 1-hexene was used as substrate. When 4-methyl-1-pentene and styrene were used as substrates, the catalytic oxidation process of TS-1/H 2 O 2 tended to occur in the straight channel, and the larger the size of the substrate, the more the oxidation reaction tends to occur in the straight channel. The above characteristics of oxidation performance are consistent with the intracrystalline diffusion characteristics of substrate molecules proposed by Derouane's group. It provides an evidence that MTC effect exists in TS-1/H 2 O 2 catalytic oxidation reaction. The proof of MTC effect is of great significance to the development of the mechanism of heterogeneous reaction process. MTC effect does exist in TS-1/H 2 O 2 catalytic oxidation system. 1-Hexene can react in both straight and sinusoidal channels. 4-Methyl-1-pentene and styrene tend to react in straight channels, and the larger the molecular size, the more the oxidation reaction tends to occur in the straight channel. • A series of TS-1 zeolites with uniform Ti atoms in the framework were successfully synthesized. • 1-Hexene reacts in both straight and sinusoidal channels. 4-Methyl-1-pentene and styrene tend to react in straight channels. • MTC effect does exist in TS-1/H 2 O 2 catalytic oxidation system.

Free‐radical catalyzed oxidation reactions with cyclohexene and cyclooctene with peroxides as initiators

AbstractThe free‐radical oxidation reaction of cyclohexene is accomplished at 80°C in a 10:1 1,2‐dichloroethane:acetonitrile mixture under an air atmosphere using 0.05 molar equivalents of either tBuOOH or H2O2 and results in a 33.7% conversion yielding 23.7% 2‐cyclohexen‐1‐one, 8.0% 2‐cyclohexen‐1‐ol, and 2.0% cyclohexene oxide. With cyclooctene under similar conditions, a 42.3% conversion is obtained, 40.3% cyclooctene oxide, 0.4% of 1,2‐cyclooctanediol, and 1.2% of 2‐cycloocten‐1‐one. The reaction is dependent on dioxygen as reduced yields are obtained under a nitrogen atmosphere. It is initiated best with H2O2 and tBuOOH and does not work with ammonium persulfate as a radical initiator. This free‐radical reaction was not useful for three other alkenes tested under similar reaction conditions. Transition states and activation energies were calculated with the APFD functional and 6‐311 + G(d) basis set for possible reaction pathways involving radicals produced from the homolysis of the peroxide OO bond followed by abstraction of an alkyl H atom, forming a cyclic alkene radical. This can react rapidly with dioxygen forming a cyclic‐alkene peroxide radical. This intermediate may result in ketone products via a unimolecular pathway, whereas the formation of epoxides requires a bimolecular route. This was confirmed experimentally as lower epoxide yields for reaction with cyclooctene were obtained if the reaction solution was diluted. It is suggested that reactions involving cyclohexene where similar yields of products were obtained may also involve free‐radical pathways.

Novel Cu-doped zeolitic imidazolate framework-8 membranes supported on copper foam for highly efficient catalytic wet peroxide oxidation of phenol

Cu-doped zeolitic imidazolate framework-8 (ZIF-8) membranes supported on three-dimensional copper foam were prepared for the first time and used for the catalytic wet peroxide oxidation of phenol in a fixed bed reactor. The properties of the new porous composite materials were studied by scanning electron microscope, energy-dispersive spectroscopy, Brunauer-Emmett-Teller surface area analysis, X-ray diffraction, thermal gravimetric analysis, Fourier-transform infrared, and X-ray photoelectron spectroscopy. The ZIF-8 membrane doped with 5% copper exhibited the best catalytic performance (the removal efficiency of phenol and H2O2 reached 100% and 95%, respectively). Reusability and stability experiments showed that a consistent complete phenol conversion and high H2O2 conversions of more than 94% were achieved using the 5% Cu-doped ZIF-8 membrane. The effects of reaction temperature, feed flow rate, and catalyst bed height on the catalytic performance were investigated to obtain the optimal reaction conditions. The material has the more economical characteristics of short reaction time, low metal loading, continuous operation, easy recycling, and good stability. The kinetics of the catalytic reaction of the Cu-doped ZIF-8 membrane were analyzed using the Power-rate Law Kinetic model. The experimental results show that the reaction is a first-order reaction, and the activation energy (Ea) of the catalyzed oxidation reaction is 66.4 kJ/mol. The initial oxidation rate equation (−rA0 = 3.24 × 108e−66400/RT CA) was obtained for Cu-doped ZIF-8 membrane–catalyzed phenol degradation.

Polyethyleneimine-assisted synthesis of ionic liquid-derived Mo-based mesoporous TiO2 composite with superior oxidative desulfurization activity

The development of fast and high yield route for large scale synthesis porous TiO2 based catalyst has attracted widespread concern in the field of optoelectronic and catalysis. Up to now, the facile synthesis of mesoporous TiO2 based composite is still limited to wet chemical synthesis approach (hydrothermal, phase transformation, or sol-gel method etc.). Here, we develop a polyethyleneimine-assisted solvent-free strategy to synthesize of ionic liquid-derived Mo-based mesoporous TiO2 composite, with molybdenum sites uniformly distributed on TiO2 matrix. As-synthesized ionic liquid-derived mesoporous MoOx/TiO2 composite is composed of uniform nano-sized anatase particles and connected by worm-like mesoporous channel. Moreover, the calcination conditions and loading amount of molybdenum-containing ionic liquid have been further optimized. These distinct characteristics endow the prospective MoOx/TiO2 composite with excellent performance in catalytic oxidation reaction, which can remove refractory organic sulfur compound in the model fuel effectively. Our work opens a new solvent-free avenue to synthesis porous metal based ionic liquids/TiO2 composite.

Rapid Discrimination of Adsorbed Oxygen and Lattice Oxygen in Catalysts by the Cataluminescence Method.

Adsorbed oxygen and lattice oxygen are crucial parameters for catalyst characterization and catalytic oxidation mechanism. Therefore, rapid discrimination of adsorbed oxygen and lattice oxygen is highly desired. Herein, a direct correlation between cataluminescence (CTL) kinetic curve and oxygen species was discovered. The adsorbed oxygen-catalyzed CTL only lasted for a few minutes, whereas the lattice oxygen-catalyzed CTL could exhibit hours of continuous luminescence. The long-term CTL was attributed to the slow migration of lattice oxygen in a slow and continuous catalytic oxidation reaction. In addition to the discrimination between the adsorbed oxygen and lattice oxygen by the CTL kinetic processes, the corresponding CTL intensity was positively proportional to their amounts. Accordingly, the developed catalytic oxidation-related CTL can be used as an indicator for rapid discrimination and determination of adsorbed oxygen and lattice oxygen in catalysts. Oxygen species detected by the proposed CTL method not only matched well with those obtained by conventional X-ray photoelectron spectroscopy and O2-temperature programmed methods but also offered some distinguished advantages, such as convenient operation, fast response, and low cost. It can be expected that the established oxygen-responsive CTL probe has great potential in distinguishing adsorbed oxygen and lattice oxygen in various catalysts.

Recent advances in catalytic oxidative reactions of phenols and naphthalenols

This critical review aims to provide an overview of oxidative phenol and naphthalenol transformations in nature and synthetic chemistry.

Tris(imidazolyl) dicopper(I) complex and its reactivity to exert the catalytic oxidation of sterically hindered phenol substrates via a [Cu2O]2+ core.

The Cu ion ligated with histidine residues is a common active site motif of various Cu-containing metalloenzymes exerting versatile catalytic oxidation reactions. Due to the scarcity of structurally characterized biomimetic binuclear Cu(I)-imidazolyl complexes, the bonding interactions between the Cu(I) center and imidazolyl donor ligands as well as their stoichiometric/catalytic oxidation reactivities remain relatively unexplored. In this study, we successfully synthesized a tris(imidazolyl) dicopper(I) complex [CuI(μ-bimeta)3CuI][PF6]2 (1) characterized by single-crystal X-ray diffraction, cyclic voltammetry, and UV-vis absorption spectroscopy. The coordination environment around each Cu(I) center of complex 1 is best described as a regular trigonal geometry and the distance between two Cu(I) centers is ∼3.0521(18) Å. From the O2-/PhIO-titration reactions of complex 1, only 0.5 equiv. of O2(g) and one equiv. of PhIO are required to produce the corresponding oxygenated product complex 1ox, respectively, exhibiting a distinct UV-vis absorption band at ∼640 nm. From the characterization of ESI mass spectrometry, IR, UV-vis spectroscopy, and O2-/PhIO-titration reactions, the molecular identity of complex 1ox is tentatively assigned as [Cu(μ-O)(μ-bimeta)3Cu]2+, which is further corroborated by the spectroscopically calibrated DFT calculations. The oxidation reactivities of complex 1ox were investigated using the well-understood sterically hindered phenol substrates DTBP and TBBP in both stoichiometric and catalytic fashions. In stoichiometric reactions, one equiv. of 1ox is capable of fully converting TBBP into TBOBF in the CH3CN solution at room temperature within 1 h. The optimized selectivity of catalytically oxidizing DTBP into TBOBF (>95% selectivity, ∼100% conversion rate) could be achieved with a 10 mol% loading of complex 1ox using air as the oxidant. From the time-course product distributions of this catalyst system, ∼40% of DTBP was converted into the corresponding TBBP product in the first 5 min. From 10 to 120 min, the oxidation of DTBP to TBBP and the oxidation of TBBP to TBOBF simultaneously proceeded, which was evidenced by the decrease of TBBP and the increase TBOBF.