Bond Oxidation Research Articles

Photocatalytic toluene oxidation with nickel-mediated cascaded active units over Ni/Bi2WO6 monolayers

Adsorption and activation of C–H bonds by photocatalysts are crucial for the efficient conversion of C–H bonds to produce high-value chemicals. Nevertheless, the delivery of surface-active oxygen species for C–H bond oxygenation inevitably needs to overcome obstacles due to the separated active centers, which suppresses the catalytic efficiency. Herein, Ni dopants are introduced into a monolayer Bi2WO6 to create cascaded active units consisting of unsaturated W atoms and Bi/O frustrated Lewis pairs. Experimental characterizations and density functional theory calculations reveal that these special sites can establish an efficient and controllable C–H bond oxidation process. The activated oxygen species on unsaturated W are readily transferred to the Bi/O sites for C–H bond oxygenation. The catalyst with a Ni mass fraction of 1.8% exhibits excellent toluene conversion rates and high selectivity towards benzaldehyde. This study presents a fascinating strategy for toluene oxidation through the design of efficient cascaded active units.

Effectiveness of sulfuric acid and hydrochloric acid catalysts in the esterification of frankincense cinnamic acid with ethanol and methanol

This research aims to compare the effectiveness of sulfuric acid and hydrochloric acid catalysts in the esterification of frankincense cinnamic acid (STYRAX paraleoncomud PERK). Esterification of sulfuric acid catalyst is carried out with ethanol and for hydrochloric acid catalyst with methanol. Esterification was carried out by refluxing a mixture of 1:20 cinnamic acid - ethanol and methanol, with 3 mL of each catalyst at a temperature of 60oC for one hour. The results were rinsed with 3 x 50 mL distilled water and dried with anhydrous sodium sulfate. The results were filtered and verified for functional groups using FTIR and composition analysis using GC – MS. The results of FTIR interpretation show a decrease in absorption intensity (-OH) at 3500 cm-1 as a functional group that reacts compared to the ester results as an indication of the ongoing esterification reaction. The resulting ethyl cinnamate has a high conversion of 84.42%. Methyl cinnamate also has a distinctive ester aroma but is clearer and based on GC-MS, the content of methyl cinnamate is relatively low, namely 34.40%, the remaining cinnamic acid is 37.28%, and various side products of 28.32%. Thus, the catalyst that provides better conversion is sulfuric acid, but it requires further purification by examining the appropriate absorbent and bleaching agent. The brown color of the ester product catalyzed by sulfuric acid is thought to occur due to the oxidation of the cinnamic acid double bond by the catalyst.

Efficient Inhibition of Deep Conversion of Partial Oxidation Products in C-H Bonds' Functionalization Utilizing O2 via Relay Catalysis of Dual Metalloporphyrins on Surface of Hybrid Silica Possessing Capacity for Product Exclusion.

To inhibit the deep conversion of partial oxidation products (POX-products) in C-H bonds' functionalization utilizing O2, 5-(4-(chloromethyl)phenyl)-10,15,20-tris(perfluorophenyl)porphyrin cobalt(II) and 5-(4-(chloromethyl)phenyl)-10,15,20-tris(perfluorophenyl)porphyrin copper(II) were immobilized on the surface of hybrid silica to conduct relay catalysis on the surface. Fluorocarbons with low polarity and heterogeneous catalysis were devised to decrease the convenient accessibility of polar POX-products to catalytic centers on the lower polar surface. Relay catalysis between Co and Cu was designed to utilize the oxidation intermediates alkyl hydroperoxides to transform more C-H bonds. Systematic characterizations were conducted to investigate the structure of catalytic materials and confirm their successful syntheses. Applied to C-H bond oxidation, not only deep conversion of POX-products was inhibited but also substrate conversion and POX-product selectivity were improved simultaneously. For cyclohexane oxidation, conversion was improved from 3.87% to 5.27% with selectivity from 84.8% to 92.3%, which was mainly attributed to the relay catalysis on the surface excluding products. The effects of the catalytic materials, product exclusion, relay catalysis, kinetic study, substrate scope, and reaction mechanism were also investigated. To our knowledge, a practical and novel strategy was presented to inhibit the deep conversion of POX-products and to achieve efficient and accurate oxidative functionalization of hydrocarbons. Also, a valuable protocol was provided to avoid over-reaction in other chemical transformations requiring high selectivity.

C-H Bond Oxidation by MnIV-Oxo Complexes: Hydrogen-Atom Tunneling and Multistate Reactivity.

The reactivity of six MnIV-oxo complexes in C-H bond oxidation has been examined using a combination of kinetic experiments and computational methods. Variable-temperature studies of the oxidation of 9,10-dihydroanthracene (DHA) and ethylbenzene by these MnIV-oxo complexes yielded activation parameters suitable for evaluating electronic structure computations. Complementary kinetic experiments of the oxidation of deuterated DHA provided evidence for hydrogen-atom tunneling in C-H bond oxidation for all MnIV-oxo complexes. These results are in accordance with the Bell model, where tunneling occurs near the top of the transition-state barrier. Density functional theory (DFT) and DLPNO-CCSD(T1) computations were performed for three of the six MnIV-oxo complexes to probe a previously predicted multistate reactivity model. The DFT computations predicted a thermal crossing from the 4B1 ground state to a 4E state along the C-H bond oxidation reaction coordinate. DLPNO-CCSD(T1) calculations further confirm that the 4E transition state offers a lower energy barrier, reinforcing the multistate reactivity model for these complexes. We discuss how this multistate model can be reconciled with recent computations that revealed that the kinetics of C-H bond oxidation by this set of MnIV-oxo complexes can be well-predicted on the basis of the thermodynamic driving force for these reactions.

The mechanism and origins of the chemo- and regio-selectivity of ruthenium porphyrin catalyzed C[sbnd]H bonds oxidation

Selective functionalization of polymers derived from branched alkane monomers is extremely challenging due to the low reactivity of CH bonds and uncontrolled depolymerization. In this work, the chemoselective and regioselective catalytic oxygenation mechanism of hydrocarbons with ruthenium porphyrin complexes and aromatic N-oxides was investigated by density functional theory (DFT) calculations. The results revealed that the oxoruthenium porphyrin species with remarkable reactivity as oxygen transfer agents is responsible for the hydrogen abstraction from CH bonds followed by fast hydroxyl radical rebound. Details regarding the calculations of various oxidation processes show that the regioselectivity is related to the intrinsic strength of different CH bonds in branched alkanes and the charge transfer of the hydrogen atom transfer (HAT) step. Comparing the oxidations of branched alkanes to alcohols and ketones, the chemoselectivity is attributed to the relative barriers of HAT pathways in the two-step oxidation stage. Finally, the substituent effects of fluorine in the porphyrin ligand are elucidated and a stronger electron-withdrawing group is predicted to promote the HAT process and regulate hydroxyl radical rebound, ultimately enabling more efficient oxidation. These findings provide relevant information for understanding the selective oxidation of polyolefins through transition metal catalysis and enzymatic catalysis.

One‐Pot Gold/Acid‐Catalyzed Synthesis of Indolo[1,2‐a]quinolin‐5(6H)‐ones from 1‐(2‐Ethynylphenyl)‐1H‐indoles

AbstractWe present a method for the synthesis of substituted indolo[1,2‐a]quinoline‐5(6H)‐ones starting from 1‐(2‐ethynylphenyl)‐1H‐indoles. The transformation involves gold‐catalyzed oxidation of the triple bond followed by acid‐promoted intramolecular cyclization at the indole C2 position. Demonstrating noteworthy versatility, the reaction tolerates a wide array of substituents on the indole core and proceeds in good to excellent yields (up to 93 %).

Oxygen-containing functional groups of activated carbon fibers as efficient oxygen transfer channels for H2S catalytic oxidation at room temperature

Activated carbon fibers (ACFs) with different activation degrees were developed by KOH activation method. And then, series of Na2CO3 loaded ACF catalysts were prepared and tested for H2S catalytic oxidation at room temperature. Among them, Na/ACF-8 presented the highest saturation sulfur capacity (1.22 gH2S/g). Importantly, it was found that COOH, COC/COH and COOCO were the main active oxygen species, and acted as oxygen transfer channels during the reaction. The reaction process mainly involved the dissociation of H2S, the reaction of HS− with C-O bond containing groups to form C-S bonds and sulfur-containing products. Moreover, the oxygen-containing functional groups were just responsible for water generation and the superoxide radical (O2•−) was responsible for SS bond oxidation. The O2•− was activated by ring carbon defects for Na/ACF-6 and Na/ACF-8 catalysts. And the ring carbon defects and ultramicropores were jointly responsible for the activation of O2•− for Na/ACF-2 and Na/ACF-4 catalysts.

Enhancing catalytic activity of UiO-66 through CuO nanoparticles incorporation: a study on Henry reaction and one-pot allylic C-H bond oxidation of olefins

Enhancing catalytic activity of UiO-66 through CuO nanoparticles incorporation: a study on Henry reaction and one-pot allylic C-H bond oxidation of olefins

Catalyst and Medium Control over Rebound Pathways in Manganese-Catalyzed Methylenic C-H Bond Oxidation.

The C(sp3)-H bond oxygenation of a variety of cyclopropane containing hydrocarbons with hydrogen peroxide catalyzed by manganese complexes containing aminopyridine tetradentate ligands was carried out. Oxidations were performed in 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) and 2,2,2-trifluoroethanol (TFE) using different manganese catalysts and carboxylic acid co-ligands, where steric and electronic properties were systematically modified. Functionalization selectively occurs at the most activated C-H bonds that are α- to cyclopropane, providing access to carboxylate or 2,2,2-trifluoroethanolate transfer products, with no competition, in favorable cases, from the generally dominant hydroxylation reaction. The formation of mixtures of unrearranged and rearranged esters (oxidation in HFIP in the presence of a carboxylic acid) and ethers (oxidation in TFE) with full control over diastereoselectivity was observed, confirming the involvement of delocalized cationic intermediates in these transformations. Despite such a complex mechanistic scenario, by fine-tuning of catalyst and carboxylic acid sterics and electronics and leveraging on the relative contribution of cationic pathways to the reaction mechanism, control over product chemoselectivity could be systematically achieved. Taken together, the results reported herein provide powerful catalytic tools to rationally manipulate ligand transfer pathways in C-H oxidations of cyclopropane containing hydrocarbons, delivering novel products in good yields and, in some cases, outstanding selectivities, expanding the available toolbox for the development of synthetically useful C-H functionalization procedures.

Chlorine radical-mediated photocatalytic C(sp3)−H bond oxidation of aryl ethers to esters

The C(sp3)−H functionalization of naturally abundant alkanes is of great importance, whereas C−H bond oxidation of aryl ethers in a redox-neutral and environmental-friendly manner remains a challenge. Herein, we report a novel method of visible-light-driven C(sp3)−H bond oxidation of aryl ethers selectively into ester products using oxygen as the oxidant. During the photocatalytic reaction using Mes-10-phenyl-Acr+−BF4− catalyst, chlorine radicals are generated from a wide variety of chloride sources and can effectively activate aryl ether C(sp3)−H bonds into alkyl radicals through the hydrogen atom transfer process. Aryl ethers with different substituents can be oxidized to esters in good to excellent yields. This work presents a new photocatalytic strategy for C(sp3)−H oxidation of aryl ethers in a convenient and green manner.

Valence Tautomerism Induced Proton Coupled Electron Transfer:X-H Bond Oxidation with a Dinuclear Au(II) Hydroxide Complex.

We report the preparation and characterization of the dinuclear AuII hydroxide complex AuII 2(L)2(OH)2 (L=N,N'-bis (2,6-dimethyl) phenylformamidinate) and study its reactivity towards weak X-H bonds. Through the interplay of kinetic analysis and computational studies, we demonstrate that the oxidation of cyclohexadiene follows a concerted proton-coupled electron transfer (cPCET) mechanism, a rare type of reactivity for Au complexes. We find that the Au-Au σ-bond undergoes polarization in the PCET event leading to an adjustment of oxidation levels for both Au centers prior to C(sp3)-H bond cleavage. We thus describe the oxidation event as a valence tautomerism-induced PCET where the basicity of one reduced Au-OH unit provides a proton acceptor and the second more oxidized Au center serves as an electron acceptor. The coordination of these events allows for unprecedented radical-type reactivity by a closed shell AuII complex.

Valence Tautomerism Induced Proton Coupled Electron Transfer:X−H Bond Oxidation with a Dinuclear Au(II) Hydroxide Complex

AbstractWe report the preparation and characterization of the dinuclear AuII hydroxide complex AuII2(L)2(OH)2 (L=N,N′‐bis (2,6‐dimethyl) phenylformamidinate) and study its reactivity towards weak X−H bonds. Through the interplay of kinetic analysis and computational studies, we demonstrate that the oxidation of cyclohexadiene follows a concerted proton‐coupled electron transfer (cPCET) mechanism, a rare type of reactivity for Au complexes. We find that the Au−Au σ‐bond undergoes polarization in the PCET event leading to an adjustment of oxidation levels for both Au centers prior to C(sp3)−H bond cleavage. We thus describe the oxidation event as a valence tautomerism‐induced PCET where the basicity of one reduced Au−OH unit provides a proton acceptor and the second more oxidized Au center serves as an electron acceptor. The coordination of these events allows for unprecedented radical‐type reactivity by a closed shell AuII complex.

Synergistic removal of dimethoate through adsorption and photocatalytic oxidation in the presence of FeTiO3@Ag/Ag2O heterojunction

Combining adsorption and photocatalysis as a synergistic technique has become a research trend since adsorption is a prerequisite for photocatalytic surface reactions. In this study, a Z-scheme heterojunction FeTiO3@Ag/Ag2O with local surface plasmon resonance (LSPR) effect was fabricated for the removal of dimethoate from water. Under visible light irradiation, dimethoate could be completely removed within 75 min in the presence of 0.3 g/L FeTiO3@Ag/Ag2O (with Ag2O percentage of 10 wt%). High removal efficiency of dimethoate was mainly attributed to the synergistic effect between the large specific surface area of the catalyst (160.695 m2/g), the formation of heterojunction of FeTiO3 and Ag2O, and the LSPR effect of metal Ag, which reinforced the absorption of visible light and promoted the separation and transfer of the carriers. Radicals of O2− and OH were the main reactive groups triggered the photocatalytic degradation process of dimethoate. Density Functional Theory (DFT) calculations indicate that PS and P–S bonds in the dimethoate molecule were more susceptible to be attacked by reactive groups. The degradation pathways mainly include oxidation of PS bond and cleavage of P–S bond, and the toxicity of most intermediates was reduced when compared with the parent compound. This study exploited the role of adsorption and photocatalysis in the field of pollutant removal, and provides ideas for the preparation of bifunctional photocatalysts.

Atomic Diffusion Engineered PtSnCu Nanoframes with High-Index Facets Boost Ethanol Oxidation.

Electrochemical ethanol oxidation is crucial to directly convert a biorenewable liquid fuel with high energy density into electrical energy, but it remains an inefficient reaction even with the best catalysts. To boost ethanol oxidation, developing multimetallic nanoalloy has emerged as one of the most effective strategies, yet faces a challenge in the rational engineering of multimetallic active-site ensembles at atomic-level. Herein, starting from typical PtCu nanocrystals, an atomic Sn diffusion strategy is developed to construct well-defined Pt47Sn12Cu41 octopod nanoframes, which is enclosed by high-index facets of n (111)-(111), such as {331} and {221}. Pt47Sn12Cu41 achieves a high mass activity of 3.10 A mg-1 Pt and promotes the C-C bond breaking and oxidation of poisonous CO intermediate, representing a state-of-the-art electrocatalyst toward ethanol oxidation in acidic electrolyte. Density functional theory （DFT） calculations have confirmed that the introduction of Sn improves the electroactivity by uplifting the d-band center through the s-p-d coupling. Meanwhile, the strong binding of ethanol and the reduced energy barrier of CO oxidation guarantee a highly efficient ethanol oxidation process with improved Faradic efficiency of C1 products. This work offers a promising strategy for constructing novel multimetallic nanoalloys tailored by atomic metal sites as the efficient electrocatalysts.

Investigating the mechanism of formation of Ca-rich Ca[sbnd]Yb apatite that forms from the Yb-silicate–CMAS reaction at 1300°C

The formation mechanism and structure of Ca-rich CaYb apatite, which forms from the corrosion of Yb-silicate based coatings with CMAS at 1300°C in air for 48 h was investigated. X-ray photoelectron spectroscopy (XPS) was used to determine the bond type and oxidation states of the apatite. XPS data showed that the Si2p peaks are related to silicates, while the Ca2p and Yb4d are linked to apatite structures. The mechanism of growth for the apatite is proposed using the Wagner-Hauffe oxidation principle and the Kröger-Vink notations. The formation mechanism of the apatite-structure reaction phase is by substitutional diffusion, which is governed by the movement (formation and destruction) of point defects within the Yb2O3 lattice, particularly oxygen vacancies and electron holes. When Ca2+ substitutes Yb3+ in its lattice position, this results in the formation of anionic vacancies, which leads to more Ca2+ diffusion. The diffusion process continues until vacancies can no longer form to achieve electroneutrality, which leads to the newly formed Yb–Ca–Si being saturated with cations. Thus, based on this investigation, it is assumed that a CaYb silicate oxyapatite coatings can suppress the vacancy formation mechanism by containing high Ca and Si content which can thus decrease the ionic diffusion from CMAS melt into the EBC lattice. This can be the premises of a more CMAS-resistant coating family.

Synthesis of α‐Imino Amidines and 2,3‐Diamino Indolenines Using a One‐Pot Graphene Oxide‐Catalyzed Process

AbstractThe acid‐catalyzed three‐component (3 C) UGI reaction of isocyanides, amines, and aldehydes generally gives α‐amino amidines. Herein, we report the graphene oxide (GO)‐promoted promoted 3 C Ugi reaction followed by a C−N bond oxidation to provide rapid access to α‐imino amidines. GO plays a crucial role both in the multicomponent reaction and in the subsequent oxidation. Interestingly, α‐imino amidines bearing electron‐donating groups undergo spontaneous cyclization leading substituted 2,3‐diamino indolenines. The scope of the process has been investigated with respect to all three components, and a comparison between the one‐pot and sequential approaches is given. The major advantages of the developed methodology include one‐pot synthesis, operational simplicity, high atom economy, broad substrate scope, multicomponent character, and applicability towards gram scale synthesis. Recovery and regeneration of GO and investigation of its real active sites has been performed by control experiments and X‐ray photoelectron spectroscopy (XPS).

Self-adjusted reaction pathway enables efficient oxidation of aromatic C–H bonds over zeolite-encaged single-site cobalt catalyst

The selective oxidation of aromatic C–H bonds to high value-added oxygenated products with molecular oxygen remains a key challenge in heterogeneous catalysis. Eligible heterogeneous catalysts are pursued and the reaction mechanism is hotly debated. Herein, we report that zeolite-encaged single-site cobalt ions can efficiently catalyze the model reaction of ethylbenzene aerobic oxidation to acetophenone, outperforming the industrial benchmark catalyst cobalt naphthenate under identical conditions. The self-accelerating phenomenon is observed in the progress of ethylbenzene aerobic oxidation, corresponding to the self-adjusted reaction pathway as revealed by kinetic studies and density functional theory calculations. The formation of reactive O* species on Co sites, resembling the well-known α-O on Fe sites, is identified to be responsible for the self-adjusted reaction pathway of aromatic C–H bond oxidation.

Construction of surface-rich MoS2 nanoflowers decorated on 2D layered MXene nanohybrid heterostructure for highly efficient and rapid degradation of oxytetracycline

In this study, we successfully developed a hybrid architecture referred to as MoS2@MX, involving the integration of MoS2 layered onto MXene using a straightforward co-precipitation method. This innovative hybrid photocatalyst exhibited remarkable efficiency in removing oxytetracycline (OTC) molecules from aqueous solutions under visible-light irradiation. During the photocatalytic process, both MoS2 and MX played distinct yet complementary roles. MoS2 facilitated efficient electron transfer, while MX contributed to the generation of radicals. This unique collaboration resulted in a noteworthy 99 % oxidation efficiency for OTC degradation within a brief 60 min of visible light exposure in an aqueous environment. The radicals 1O2 and •OH were identified as the principal drivers behind OTC degradation, underscoring the vital role of the hybrid material. Mechanistically, the degradation of OTC involved several key steps, including C–H bond cleavage, de-carboxylation, C–N bond oxidation, and de-chlorination. Importantly, the MoS2@MX hybrid composite demonstrated remarkable stability, maintaining a noteworthy photocatalytic efficiency of 89 % for targeted OTC removal after undergoing five consecutive cycles. In conclusion, this study emphasizes the potential of the MoS2@MX hybrid material as an effective agent for degrading organic OTC compounds within aquatic environments. The hybrid's multifaceted roles and exceptional performance suggest promising applications in sustainable water treatment.

First‐Row Transition‐Metal Complexes with Tetra‐Amido Macrocyclic Ligands for Water and C(sp3)−H Bond Oxidation: Performance Benchmarking Using Free Energy Relationships

AbstractThe catalytic oxidation of water and C(sp3)−H bonds enables the conversion of solar/electrochemical energy into chemical energy and alcohol fuel production, respectively, and therefore plays important roles in energy conversion/storage. These transformations are typically catalyzed by the highly active complexes of the earth‐abundant first‐row transition metals (Mn, Fe, Co, Ni, and Cu) with tetra‐amido macrocyclic ligands (TAMLs), although the related kinetics and thermodynamics remain underexplored. This review uses free energy relationships between kinetic and thermodynamic descriptors as normalized metrics to benchmark/compare these TAML‐based catalysts and assess the advances in their development.

Sustainable Aerobic Allylic C-H Bond Oxidation with Heterogeneous Iron Catalyst.

Emerging techniques are revolutionizing the realm of chemical synthesis by introducing new avenues for C-H bond functionalization, which have been exploited for the synthesis of pharmaceuticals, natural compounds, and functional materials. Allylic C-H bond oxidation of alkenes serves as possibly the most employed C-H bond functionalization reaction. However, sustainable and selective approaches remain scarce, and the majority of the existing conditions still hinge on hazardous oxidants or costly metal catalysts. In this context, we introduce a heterogeneous iron catalyst that addresses the above-mentioned concerns by showcasing the aerobic oxidation of steroids, terpenes, and simple olefins to the corresponding enone products. This novel method provides a powerful tool for the arsenal of allylic C-H bond oxidation while minimizing the environmental concerns.