Catalytic Conditions Research Articles

Single-Atom Catalysts on Covalent Organic Frameworks for Energy Applications.

Single-atom catalysts (SACs) have been investigated and applied to energy conversion devices. However, issues of metal agglomeration, low metal loading, and substrate stability have hindered realization of the SACs' full potential. Recently, covalent organic framework (COF)-based SACs have emerged as promising materials to enable highly efficient catalytic reactions. Here, we summarize the representative COF-based SACs and their wide application in clean energy devices and conversion reactions, such as hydrogen evolution reaction, carbon dioxide reduction reaction, nitrogen reduction reaction, oxygen reduction reaction, and oxygen evolution reaction. Based on their catalysis conditions, these reactions are categorized into photocatalyzed and electrocatalyzed reactions. We also summarize their design strategies, including heteroatom inclusion, donor-acceptor pairs, pore engineering, interface engineering, etc. Although COF-based SACs are promising, more efforts, such as linkage engineering, functional groups, ionization, multifunctional sites for cocatalyzed systems, etc., could improve them to be the ideal SAC materials. At the end, we provide our perspectives on where the field will proceed in the next 5 years.

Dual Nickel- and Photoredox-Catalyzed Asymmetric Reductive Cross-Coupling To Access Chiral Secondary Benzylic Alcohols.

Transition-metal-catalyzed asymmetric cross-coupling represents a powerful strategy for C-C bond formation and the synthesis of enantiomerically pure molecules. Here, we report a dual nickel/photoredox-catalyzed enantioselective reductive cross-coupling of aryl halides with α-bromobenzoates, readily generated from aliphatic aldehydes, to provide diverse chiral secondary benzylic alcohols that are important motifs in bioactive natural products and pharmaceuticals. This dual catalytic system features mild conditions, good functional group tolerance, broad substrate scope, excellent enantiocontrol, and avoidance of stoichiometric metal reductants, presenting great potential for late-stage functionalization of complex molecules.

Quantitative Determination of Active Species Transforming the R-NHC Coupling Process under Catalytic Conditions.

Palladium complexes with N-heterocyclic carbenes (Pd/NHC) serve as prominent precatalysts in numerous Pd-catalyzed organic reactions. While the evolution of Pd/NHC complexes, which involves the cleavage of the Pd-C(NHC) bond via reductive elimination and dissociation, is acknowledged to influence the catalysis mechanism and the performance of the catalytic systems, conventional analytic techniques [such as NMR, IR, UV-vis, gas chromatography-mass spectrometry (GC-MS), and high-performance liquid chromatography (HPLC)] frequently fail to quantitatively monitor the transformations of Pd/NHC complexes at catalyst concentrations typical of real-world conditions (below approximately 1 mol %). In this study, for the first time, we show the viability of using electrospray ionization mass spectrometry (ESI-MS). This approach was combined with the use of selectively deuterated H-NHC, Ph-NHC, and O-NHC coupling products as internal standards, allowing for an in-depth quantitative analysis of the evolution of Pd/NHC catalysts within actual catalytic systems. The reliability of this approach was affirmed by aligning the ESI-MS results with the NMR spectroscopy data obtained at greater Pd/NHC precatalyst concentrations (2-5 mol %) in the Mizoroki-Heck, Sonogashira, and alkyne transfer hydrogenation reactions. The efficacy of the ESI-MS methodology was further demonstrated through its application in the Mizoroki-Heck reaction at Pd/NHC loadings of 5, 0.5, 0.05, and 0.005 mol %. In this work, for the first time, we present a methodology for the quantitative characterization of pivotal catalyst transformation processes commonly observed in M/NHC systems.

Electrochemical bromination of electron-rich compounds employing LiBr as a “Br” source

A direct electrochemical-mediated CH bromination strategy of electron-rich compound is established using LiBr as a “Br” source under transition metal-free and oxidant-free catalysis condition. This method is performed in a green and sustainable system. A wide range of electron-rich compounds were found to be compatible, providing the corresponding products with moderate yields.

Radical-Mediated Decarboxylative C-C and C-S Couplings of Carboxylic Acids via Iron Photocatalysis.

Despite the significant success of decarboxylative radical reactions, the catalytic systems vary considerably upon different radical acceptors, requiring renewed case-by-case reaction optimization. Herein, we developed an iron catalytic condition that enables the highly efficient decarboxylation of various carboxylic acids for a range of radical transformations. This operationally simple protocol was amenable to a wide array of radical acceptors, delivering structurally diverse oxime ethers, alkenylation, alkynylation, thiolation, and amidation products in useful to excellent yields (>40 examples, up to 95% yield).

Generation and Reactivity of μ-1,2-Peroxo CuIICuII and Bis-μ-oxo CuIIICuIII Species and Catalytic Hydroxylation of Benzene to Phenol with Hydrogen Peroxide.

Tetradentate-N4 ligands stabilize dinuclear {CuII(μ-1,2-peroxo)CuII} and {CuIII(μ-O)2CuIII} species, and CuII complexes of these ligands were reported to catalyze the oxidation of benzene with H2O2. Here, we report {CuII(μ-1,2-peroxo)CuII} and {CuIII(μ-O)2CuIII} intermediates of dinucleating bis(tetradentate-N4) ligands depending on the absence or presence of 6-methyl substituents on the terminal pyridine donors, respectively, generated either from {CuICuI} precursors with O2 or from {CuIICuII} precursors with H2O2 and NEt3. Both intermediates are not stable even at low temperatures, but they show no electrophilic HAT reactivity with DHA. Catalytic investigations on the hydroxylation of benzene with excess H2O2 between 30 and 50 °C indicate that both radical-based and {Cu2On}-based mechanisms depend strongly on the catalytic conditions. In the presence of a radical scavenger, TONs of ∼920/∼720 have been achieved without/with the 6-methyl group of the ligand. Although {CuII(μ-OH)CuII} reacts with excess H2O2 at -40 °C to {CuII(OOH)}2 species, these are only stable for seconds at 20 °C and cannot account for catalytic oxidations over a period of 24 h at 30-50 °C.

CO Oxidation Promoted by NO Adsorption on RhMn2O3- Cluster Anions.

CO oxidation represents an important model reaction in the gas phase to provide a clear structure-reactivity relationship in related heterogeneous catalysis. Herein, in combination with mass spectrometry experiments and quantum-chemical calculations, we identified that the RhMn2O3- cluster cannot oxidize CO into gas-phase CO2 at room temperature, while the NO preadsorbed products RhMn2O3-[(NO)1,2] are highly reactive in CO oxidation. This discovery is helpful to get a fundamental understanding on the reaction behavior in real-world three-way catalytic conditions where different kinds of reactants coexist. Theoretical calculations were performed to rationalize the crucial roles of preadsorbed NO where the strongly attached NO on the Rh atom can greatly stabilize the products RhMn2O2-[(NO)1,2] during CO oxidation and at the same time works together with the Rh atom to store electrons that stay originally in the attached CO2- unit. The leading result is that the desorption of CO2, which is the rate-determining step of CO oxidation by RhMn2O3-, can be greatly facilitated on the reactions of RhMn2O3-[(NO)1,2] with CO.

Oxidation State‐Based Selectivity Tuning in Transition Metal Catalysis

AbstractTuning between different selectivity is a challenging yet promising aspect in transition metal catalysis. Traditional methods for the attainment of synthetically relevant products rely on changing the solvent, ligand or additive. Despite the existing examples, outcomes of new catalytic conditions remain elusive. Recently, a novel tuning strategy based on the oxidation state of metal has drawn our attention. This method highlights the difference in reaction pathways, exhibiting great potential for high predictability. Nonetheless, researches within this field are scarcely‐reported in the present literature, and many of which show limitations in the elucidation of mechanism. To fully handle this tactic, more in‐depth investigations are demanded.

Mechanism of Alkene Hydrofunctionalization by Oxidative Cobalt(salen) Catalyzed Hydrogen Atom Transfer.

Oxidative MHAT hydrofunctionalization of alkenes provides a mild cobalt-catalyzed route to forming C-N and C-O bonds. Here, we characterize relevant salen-supported cobalt complexes and their reactions with alkenes, silanes, oxidant, and solvent. These stoichiometric investigations are complemented by kinetic studies of the catalytic reaction and catalyst speciation. We describe the solution characterization of an elusive cobalt(III) fluoride complex, which surprisingly is not the species that reacts with silane under catalytic conditions; rather, a cobalt(III) aquo complex is more active. Accordingly, the addition of water (0.15 M) speeds the catalytic reaction, and kinetic studies show that water addition enables catalytic product formation in 2 h at -50 °C in acetone. Under these conditions, cobalt(III) resting states can be observed by UV-vis spectrophotometry, including a cobalt(III)-alkyl complex. It comes from a transient cobalt(III) hydride complex that is formed in the turnover-limiting step of the catalytic cycle. This hydride readily degrades but not to H2; it releases H+ through a bimetallic pathway that explains the [Co]2 dependence of the off-cycle reaction. In contrast, the rate of the catalytic reaction follows the power law kobs[Co]1[silane]1. Because of the different [Co] dependence of the catalytic reaction and the degradation reaction, lower catalyst loading improves the yield of the catalytic reaction by reducing the relative rate of unproductive silane/oxidant consumption. These studies illuminate mechanistic details of oxidative MHAT hydrofunctionalization of alkenes and lay the groundwork for understanding other catalytic reactions mediated by cobalt hydride and cobalt alkyl complexes.

Sustainable production of triazoles from lignin major motifs.

An efficiently catalyzed synthesis of pharmaceutically relevant 1,2,3-trazoles from renewable resources is highly desirable. However, due to incompatible catalysis conditions, this endeavor remained challenging so far. Herein, a practical access protocol to 1,2,3-triazoles, starting from lignin phenolic β-O-4 with γ-OH group utilizing a vanadium-based catalyst is presented. A broad substrate scope reaching up to 97 % yield of 1,2,3-triazoles are obtained. The reaction pathway includes selective cleavage of double C-O bonds, cycloaddition, and dehydrogenation. Mechanistic studies and density-functional theory (DFT) calculations suggest that the V-based complex acts as a bifunctional catalyst for both selective C-O bonds cleavage and dehydrogenation. This synthetic pathway has been applied for the synthesis of pharmacological and biological active carbohydrate derivatives starting from biomass components as feedstock, enabling a potential sustainable route to triazolyl carbohydrate derivatives, which paves the way for lignin-based heterocyclic aromatics in the pharmaceutical applications.

Dynamic in situ Formation of Cu2O Sub‐Nanoclusters through Photoinduced pseudo‐Fehling's Reaction for Selective and Efficient Nitrate‐to‐Ammonia Photosynthesis

AbstractCopper (Cu) is evidenced to be effective for constructing advanced catalysts. In particular, Cu2O is identified to be active for general catalytic reactions. However, conflicting results regarding the true structure‐activity correlations between Cu2O‐based active sites and efficiencies are usually reported. The structure of Cu2O undergoes dynamic evolution rather than remaining stable under working conditions, in which the actual reaction cannot proceed over the prefabricated Cu2O sites. Therefore, the dynamic construction of Cu2O active sites can be developed to promote catalytic efficiency and reveal the true structure‐activity correlations. Herein, by introducing the redox pairs of Cu2+ and reducing sugar into a photocatalysis system, it is clarified that the Cu2O sub‐nanoclusters (NCs), working as novel active sites, are on‐site constructed on the substrate via a photoinduced pseudo‐Fehling's route. The realistic interfacial charge separation and transformation capacities are remarkably promoted by the dynamic Cu2O NCs under the actual catalysis condition, which achieves a milestone efficiency for nitrate‐to‐ammonia photosynthesis, including the targets of production rate (1.98±0.04 mol gCu−1 h−1), conversion ratio (94.2±0.91 %), and selectivity (98.6 %±0.55 %). The current work develops an effective strategy for integrating the active site construction into realistic reactions, providing new opportunities for Cu‐based chemistry and catalysis sciences research.

Dynamic in situ Formation of Cu2 O Sub-Nanoclusters through Photoinduced pseudo-Fehling's Reaction for Selective and Efficient Nitrate-to-Ammonia Photosynthesis.

Copper (Cu) is evidenced to be effective for constructing advanced catalysts. In particular, Cu2 O is identified to be active for general catalytic reactions. However, conflicting results regarding the true structure-activity correlations between Cu2 O-based active sites and efficiencies are usually reported. The structure of Cu2 O undergoes dynamic evolution rather than remaining stable under working conditions, in which the actual reaction cannot proceed over the prefabricated Cu2 O sites. Therefore, the dynamic construction of Cu2 O active sites can be developed to promote catalytic efficiency and reveal the true structure-activity correlations. Herein, by introducing the redox pairs of Cu2+ and reducing sugar into a photocatalysis system, it is clarified that the Cu2 O sub-nanoclusters (NCs), working as novel active sites, are on-site constructed on the substrate via a photoinduced pseudo-Fehling's route. The realistic interfacial charge separation and transformation capacities are remarkably promoted by the dynamic Cu2 O NCs under the actual catalysis condition, which achieves a milestone efficiency for nitrate-to-ammonia photosynthesis, including the targets of production rate (1.98±0.04 mol gCu -1 h-1 ), conversion ratio (94.2±0.91 %), and selectivity (98.6 %±0.55 %). The current work develops an effective strategy for integrating the active site construction into realistic reactions, providing new opportunities for Cu-based chemistry and catalysis sciences research.

Affinity-assisted covalent self-assembly of PduQ-SpyTag and Nox-SpyCatcher to construct multi-enzyme complexes on the surface of magnetic microsphere modified with chelated Ni2+

It is of great significance to study the effect of multi-enzyme aggregation behavior at the interface on the formation of multi-enzyme complexes and their co-catalytic characteristics, which is helpful for us to design and construct immobilized multi-enzyme complex systems for in vitro synthetic biology. Here, a magnetic microsphere with chelated Ni2+, was prepared to explore the self-assembly characteristics of PduQ-SpyTag (P-T) and Nox-SpyCatcher (NC) on its surface, based on the mixed interaction mode consisting the affinity of His-tag/Ni2+ and covalent binding of SpyTag/SpyCatcher. After studying the effect of saturated or unsaturated adsorption of P-T on the covalent binding between P-T and NC at the interface, a possible multienzyme interaction mechanism for the affinity-assisted covalent self-assembly on the Ni2+ chelating surface was proposed. The time evolution of NADH showed that the immobilized P-T/N-C complex formed by this method and the free P-T/N-C complex exhibited similar synergistic catalytic properties, and presented higher catalytic efficiency than the simple mixing of P-T and NC. The optimal catalytic conditions, stability and reusability of the immobilized multi-enzyme complexes prepared in this study were also discussed by comparing them with free enzymes. In this study, we demonstrate a simple and effective strategy for self-assembling SpyTag/SpyCatcher fusion proteins on the surface of magnetic beads, which is inspiring for the construction of more cascade enzyme systems at the interface. It provides a new method for facilitating the rapid construction of immobilized multi-enzyme complexes in vitro from the crude cell lysis.

TiO2/SiC supported catalyst for efficient thermocatalytic conversion of SF6 waste gas

The harmless treatment of SF6 waste gas is currently a highly concerned focus in the power industry. This article used a new supported catalyst, TiO2/SiC, to study the thermocatalytic conversion of SF6 waste gas. Firstly, the catalytic activity of TiO2/SiC was tested, and it was found that the catalytic efficiency of TiO2/SiC was 3.73 times that of TiO2 at 700 °C; Subsequently, the optimal catalytic conditions for TiO2/SiC were figured out by experiments, which were conducted under different initial pressures and oxygen concentrations. It was found that the catalytic efficiency of TiO2/SiC was highest when the initial pressure was 0.16 MPa and the concentration rate of SF6 and O2 was 1:4. Under these conditions, the total conversion of SF6 by TiO2/SiC reached 288 ml in 6 h, and the average catalytic conversion efficiency reached 33 ml g−1 h−1. It was also found that when the conversion of SF6 reached 110–130 ml, the catalytic activity of TiO2/SiC decreased; the oxygen concentration has a significant influence on the products: the higher the oxygen concentration is, the higher the production of SO2F2 rate in the product, while the lower that of SO2 rate. Finally, in order to know the catalytic mechanism of TiO2/SiC, XPS tests were conducted on the catalysts before and after the experiment. According to the XPS spectrum, gaseous products would react with TiO2 and generate TiF4 and Ti(SO4)2. According to the test results, the catalytic mechanism of TiO2/SiC was summarized in this article. It explained the catalytic effect of TiO2/SiC from two aspects: promoting the defluorination of SF6 and consuming low-fluorinated sulfides. The empirical conclusions of this article provide a theoretical reference for the harmless treatment of SF6 waste gas.

Silyloxymethylation of Aryl Halides via Metallaphotoredox Catalyzed Desulfinative Cross‐Coupling with Silyl Rongalite

AbstractA visible‐light‐triggered silyloxymethylation of aryl halides has been developed by the merger of photoredox and transition metal catalysis. Under the Ru/Ni dual catalytic conditions, sodium tert‐butyl‐dimethylsilyloxymethanesulfinate (SOMS) undergoes facile extrusion of sulfur dioxide to engender a silyloxymethyl radical that engages in the cross‐coupling with a range of aryl halides to produce benzyl silyl ether derivatives. The protocol is also effective with alkenyl halides and triflates, thus offering an efficient synthetic approach to the silyl‐protected allylic alcohols.

PVP−I Catalyzed Oxidation of N‐substituted Benzylamines to Benzamides

AbstractAn oxidative transformation from N‐substituted benzylamine into the corresponding benzamides was developed here using the oxidative system combined from the catalytic amount of PVP−I (polyinyl pyrrolidone) with TBHP. This newly developed method had the advantages of mild reaction conditions and broad substrate scope. The key intermediate of Enzalutamide as androgen receptor inhibitors was prepared using this catalytic condition starting from commercial available 2‐fluoro‐4‐nitrobenzaldehyde with the yield of 78.5 % for three‐step reactions.

Decomposition of methanol-d4 on Rh nanoclusters supported by thin-film Al2O3/NiAl(100) under near-ambient-pressure conditions.

The decomposition of methanol-d4 (CD3OD) on Rh nanoclusters grown by the deposition of Rh vapors onto an ordered thin film of Al2O3/NiAl(100) was studied, with various surface-probe techniques and largely under near-ambient-pressure (NAP) conditions. The results showed a superior reactivity of small Rh clusters (diameter < 1.5 nm) exposed to CD3OD at 5 × 10-3-0.1 mbar at 400 K; the gaseous production of CO and D2 from decomposed methanol-d4 per Rh surface site on the small Rh clusters with diameters of ∼1.1 nm was nearly 8 times that on large ones with diameters of ∼3.5 nm. The promotion of reactivity with decreased cluster size under NAP conditions was evidently greater than that under ultrahigh vacuum conditions. Moreover, the concentration of atomic carbon (C*; where * denotes adsorbate)-a key catalyst poisoner-yielded from the dissociation of CO* from dehydrogenated methanol-d4 was significantly smaller on small clusters (diameter < 1.5 nm). The NAP size effect on methanol-d4 decomposition involved the surface hydroxyl (OH*) from the little co-adsorbed water (H2O*) that was dissociated at a probability dependent on the cluster size. H2O* was more likely dissociated into OH* on small Rh clusters, by virtue of their more reactive d-band structure, and the OH* then effectively promoted the O-D cleavage of methanol-d4, as the rate-determining step, and thus the reaction probability; on the other hand, the OH* limited CO* dissociation on small Rh clusters via both adsorbate and lateral effects. These results suggest that the superior properties of small Rh clusters in both reactivity and anti-poisoning would persist and be highly applicable under "real-world" catalysis conditions.

Axial ligand-induced high electrocatalytic hydrogen evolution activity of molecular cobaloximes in homo- and heterogeneous medium.

Three new molecular cobaloxime complexes with the general formula [ClCo(dpgH)2L] (1-3), where L1 = N-(4-pyridylmethyl)-1,8-naphthalimide, L2 = 4-bromo-N-(4-pyridylmethyl)-1,8-naphthalimide, L3 = 4-piperidin-N-(4-pyridylmethyl)-1,8-naphthalimide, have been synthesized and characterized by UV-Vis, multinuclear NMR, FT-IR and PXRD spectroscopic techniques. The crystal structures of all complexes have also been reported. The electrocatalytic activity of complexes is investigated under two catalysis conditions: (i) homogeneous conditions in acetonitrile using acetic acid (AcOH) as a proton source and (ii) heterogeneous conditions upon immobilization onto the surface of activated carbon cloth (CC). Complex 3 exhibited high electrocatalytic HER activity under both homogeneous and heterogeneous conditions. It catalyses proton reduction to molecular hydrogen in acetonitrile solution at a lower overpotential (640 mV) with a high turnover frequency (TOF) of 524.57 s-1 and demonstrates good stability in acidic conditions. Furthermore, catalytic (working) electrodes are prepared by immobilizing the complexes onto the surface of activated carbon cloth (CC) for electrocatalytic HER under heterogeneous conditions. An impressive HER performance was again obtained with catalytic electrode 3@CC in 1.0 M KOH, achieving a current density of -10 mA cm-2 at an overpotential of 262 mV. Chronoamperometric (CA) studies showed no significant decay of the initial current density for 10 h, indicating the excellent stability of 3@CC. Additionally, UV-Vis and NMR spectral studies of the recovered catalyst after electrocatalysis revealed no structural changes, demonstrating its robustness under reaction conditions.

The importance of understanding (pre)catalyst activation in versatile C-H bond functionalisations catalysed by [Mn2(CO)10

Mn-catalysed reactions offer great potential in synthetic organic and organometallic chemistry and the success of Mn carbonyl complexes as (pre)catalysts hinges on their stabilisation by strong field ligands enabling Mn(i)-based, redox neutral, catalytic cycles. The mechanistic processes underpinning the activation of the ubiquitous Mn(0) (pre)catalyst [Mn2(CO)10] in C-H bond functionalisation reactions is now reported for the first time. By combining time-resolved infra-red (TRIR) spectroscopy on a ps-ms timescale and in operando studies using in situ infra-red spectroscopy, insight into the microscopic bond activation processes which lead to the catalytic activity of [Mn2(CO)10] has been gained. Using an exemplar system, based on the annulation between an imine, 1, and Ph2C2, 2, TRIR spectroscopy enabled the key intermediate [Mn2(CO)9(1)], formed by CO loss from [Mn2(CO)10], to be identified. In operando studies demonstrate that [Mn2(CO)9(1)] is also formed from [Mn2(CO)10] under the catalytic conditions and is converted into a mononuclear manganacycle, [Mn(CO)4(C^N)] (C^N = cyclometallated imine), a second molecule of 1 acts as the oxidant which is, in turn, reduced to an amine. As [Mn(CO)4(C^N)] complexes are catalytically competent, a direct route from [Mn2(CO)10] into the Mn(i) catalytic reaction coordinate has been determined. Critically, the mechanistic differences between [Mn2(CO)10] and Mn(i) (pre)catalysts have been delineated, informing future catalyst screening studies.

P(V)-bis(amidophenolate) ligand cooperation: stoichiometric CO-bond cleavage in aldehydes and ketones.

The cooperation between a geometrically constrained, highly electrophilic phosphorus(V) center, and an electronically rich tetradentate bis(amidophenolate) ligand enables the cleavage of the CO bond from typical aldehydes and ketones delivering iminio phosphoramidate species. The amphiphilic nature of these products, which is demonstrated through their reaction with typical Lewis acids and bases, enables their use as a mild source of silylium cations from silanes, allowing the selective reductive coupling of aldehydes to ethers under catalytic conditions.