Metal Reduction Research Articles

Dual Photoredox and Titanium Catalyzed Regioselective Allenylation of Aldehydes via Reductive Radical‐Polar Crossover

Comprehensive SummaryThe direct reductive coupling of carbonyl compounds with propargyl halides is a powerful and reliable tool in the synthesis of α‐allenols. However, stoichiometric metal reductants, harsh reaction conditions and a variety of additional additives are required in the traditional strategies. Additionally, the reactivity and regioselectivity control remains an elusive challenge. Herein, we developed the Ti‐catalyzed regioselective reductive coupling of readily available aldehydes and racemic propargyl bromides to rapidly access a wide range of α‐allenols. This method proceed efficiently in a reductive radical‐polar crossover manner featuring mild conditions, excellent regioselectivity control, broad substrate scope, and eco‐friendliness. Preliminary mechanistic studies support the radical‐involved catalytic cycle. And the DFT calculations demonstrate that the regioselectivity is determined by the Zimmerman‐Traxler‐type transition states.

Z-scheme driven charge transfer in g-C3N4/α-Fe2O3 nanocomposites enabling photocatalytic degradation of crystal violet and chromium reduction

In this study, we demonstrated the design and fabrication of iron oxide-embedded protonated graphitic carbon nitride (α-Fe2O3/p-g-C3N4) nanocomposites for photocatalytic dye degradation and heavy metal reduction applications under sunlight irradiation. The developed nanocomposites, with varying weight percentages of α-Fe2O3, were characterized for their structural (XRD, FTIR, XPS), optical (absorption and photoluminescence), morphological (FE-SEM, TEM), and electrochemical (EIS) properties to elucidate their structure-property relationships. The synthesis method ensures the uniform dispersion of α-Fe2O3 nanoparticles, with a particle size range of 50–60 nm, onto p-g-C3N4. XPS analysis suggests the formation of an electrical layer at the interface of α-Fe2O3/p-g-C3N4, facilitating the formation of a Z-scheme heterojunction. The photoluminescence and EIS spectra of the nanocomposite indicated effective separation and transfer of photo-induced charge carriers, aided by a reduced bandgap energy of ∼2.63 eV. Notably, the optimized 10 wt% α-Fe2O3/p-g-C3N4 nanocomposite exhibited superior photocatalytic activity, degrading nearly 100 % of crystal violate dye and reducing 98 % of Cr(VI) ions, compared to bare p-g-C3N4, which degraded around 43 % of the dye and reduced 39 % of Cr(VI) ions under sunlight irradiation. Scavenger studies indicated that α-Fe2O3/p-g-C3N4 nanocomposites produce adequate superoxide anions and hydroxyl radicals for dye degradation and heavy metal ion reduction. The composite also demonstrated consistent recyclability up to 5 cycles with around 100 % cyclical efficiency. The pH-dependent photoreduction and cyclic dye degradation by the 10 wt% α-Fe2O3/p-g-C3N4 photocatalyst indicated excellent stability, making it suitable for the treatment of multi-pollutant wastewater.

Microbial fuel cells: A potent and sustainable solution for heavy metal removal

The global water pollution problem is becoming increasingly crucial. One of the major contributors to water pollution is the presence of heavy metals. Heavy metals pose significant threat to both humans and all ecosystems. Various factors influence the removal of heavy metals from wastewater, including pH, temperature, natural organic matter (NOM), and ionic strength, which vary based on the chemical properties of the pollutants. More effective and modern approaches receive attention and extensively researched to substitute traditional methods such as adsorption, membrane filtration, and chemical-based separation. Among these methods, Microbial fuel cells (MFCs) are particularly intriguing. This review article focuses on MFCs and their potential applications in various fields, including clean water production. MFCs represent an innovative technology that not only generates electricity, but also demonstrates significant potential for heavy metal removal from wastewater. Cathodic chamber of MFCs effectively reduces heavy metals, while organic substrates act as carbon and electron donors in the anodic chamber. Through various mechanisms, including direct and indirect metal reduction, biofilm formation (metal sequestering), electron shuttling, and synergistic interactions among microbial communities, microorganisms exhibit remarkable efficiency in removing metals. Studies showed that dual- and single-chamber MFCs could efficiently remove a range of heavy metals, including chromium, cobalt, copper, vanadium, mercury, gold, selenium, lead, magnesium, manganese, zinc, and sodium, while simultaneously generating electricity, achieving high removal efficiencies ranging from 25% to 99.95%. This range of efficiency varies depending on the specific contaminant being targeted, the concentration of the contaminant, as well as the operating conditions such as pH and temperature. Moreover, MFCs demonstrated a wide range of power outputs, typically ranging from 0.15 W/m² to 6.58 W/m², depending on the specific configuration and conditions. These findings underscore the potential of MFCs as a sustainable and efficient approach for both wastewater treatment and energy generation.

Modular Synthesis of Heterobenzylic Amines via Carbonyl Azinylative Amination.

Transformations enabling the synthesis of α-alkyl, α'-2-azinyl amines by addition of 2-heteroaryl-based nucleophiles to in situ-generated and non-activated alkyl-substituted iminium ions are extremely rare. Approaches involving classical 2-azinyl organometallics, such as the corresponding Grignard reagents, often fail to produce the desired products. Here, we report an operationally straightforward solution to this problem through the development of a multicomponent coupling process wherein a soft 2-azinyl indium nucleophile, generated in situ from the corresponding 2-iodo heteroarene and indium powder, adds to an iminium ion that is also formed directly in the reaction. This modular carbonyl azinylative amination (CAzA) displays a broad scope and only a metal reductant is needed to generate a reactive 2-azinyl nucleophile. Beyond the addition to iminium ions, the 2-azinyl addition to polyfluoromethyl ketones forms the corresponding tertiary alcohols. Together, the products of these reactions possess a high degree of functionality, are typically challenging to synthesize by other methods, and contain motifs recognized as privileged in the context of pharmaceuticals and agrochemicals.

Biaryl Anion Radical Formation by Potassium Metal Reduction of Aryl Isocyanates and Triaryl Isocyanurates.

The potassium metal reduction of aryl isocyanates (aryl = phenyl, p-tolyl, 3,5-dimethylphenyl, 4-biphenylyl, and 1-naphthyl) in THF with 18-crown-6 or in HMPA results in the formation of the corresponding triaryl isocyanurate anion radicals. Continued exposure to potassium results in loss of the isocyanurate anion radical and the eventual formation of the respective biaryl anion radical. The 1,1'-binaphthyl anion radical is found to undergo a cyclodehydrogenation reaction, which leads to formation of the perylene anion radical. When authentic triaryl isocyanurates are reduced with metal, the heterocyclic ring undergoes fragmentation with elimination of carbon monoxide to produce a triarylbiuret dianion. This ring opening reaction is initiated by the two-electron reduction of the neutral isocyanurate species. The biaryl anion radical is formed when the biuret dianion is reduced further with metal. A possible mechanism for biaryl formation involves a heterolytic cleavage of an aryl C-N bond and release of an aryl radical once the triarylbiuret dianion is further reduced. A subsequent intermolecular reaction between two aryl radicals forms the corresponding biaryl, which can then be reduced to the anion radical. Notably, when a mixture of two different triaryl isocyanurate compounds is reduced in solution, the corresponding mixed biaryl anion radical is generated.

Synthetic Challenges toward Modeling Formate Dehydrogenases Using [WVI≡S] Complexes Supported by a Tetradentate [N2S2]4- Ligand.

This report documents our attempts at synthesizing a terminal [WVI≡S] complex supported by a tetradentate, diamido/dithiolate ligand ([N2S2]4-). The target compound was selected because it would serve as a synthetic model for the active sites of formate dehydrogenase (FDH) enzymes. Although the desired [N2S2]WVI≡S species was observed as an NEt3 adduct by mass spectrometry in one case, generally unwanted side reactions prevented isolation and definitive characterization of the target compound. Instead, isolated products characterized by X-ray crystallography included {[N2S2]H}WVI(S2)Cl from redox chemistry of the terminal sulfide, ([N2S2]WVI)2(μ-[N2S2]) from dissociation of the terminal sulfide, ({[N2S2]H}WV)2(μ-S)2 from metal reduction and μ-sulfide bridge formation, and {[N2S2]H}2 from disulfide bond formation via thiolate redox chemistry. A product formed from adventitious exposure to air/moisture, {[N2S2]H2}WVI(O)2, was also characterized. The diverse range of products formed simply from attempted metalation of the [N2S2]4- ligand with Cl4WVI≡S highlights the synthetic challenges toward building active sites that are structurally faithful to FDH.

Synthesis of metallic nanoparticles using biometabolites: mechanisms and applications.

Bio-metabolites have played a crucial role in the recent green synthesis of nanoparticles, resulting in more versatile, safer, and effective nanoparticles. Various primary and secondary metabolites, such as proteins, carbohydrates, lipids, nucleic acids, enzymes, vitamins, organic acids, alkaloids, flavonoids, and terpenes, have demonstrated strong metal reduction and stabilization properties that can be utilized to synthesize nanomaterials and influence their characters. While physical and chemical methods were previously used to synthesize these nanomaterials, their drawbacks, including high energy consumption, elevated cost, lower yield, and the use of toxic chemicals, have led to a shift towards eco-friendly, rapid, and efficient alternatives. Biomolecules act as reducing agents through deprotonation, nucleophilic reactions, transesterification reactions, ligand binding, and chelation mechanisms, which help sequester metal ions into stable metal nanoparticles (NPs). Engineered NPs have potential applications in various fields due to their optical, electronic, and magnetic properties, offering improved performance compared to bulkier counterparts. NPs can be used in medicine, food and agriculture, chemical catalysts, energy harvesting, electronics, etc. This review provides an overview of the role of primary and secondary metabolites in creating effective nanostructures and their potential applications.

Nickel/Photoredox-Catalyzed Asymmetric Three-Component Cross-Coupling To Access Enantioenriched 1,1-Diaryl(heteroaryl)alkanes.

An enantioselective 1,2-dicarbofunctionalization of vinyl (hetero)arenes with alkyl bromides and aryl bromides through nickel/photoredox catalysis is described. This three-component enantioselective domino alkyl arylation of vinyl (hetero)arenes could generate a diverse array of enantioenriched 1,1-diaryl(heteroaryl)alkanes with good to excellent yields (up to 88%) and high enantioselectivities (up to 99% ee). This transformation could proceed well under mild conditions with excellent chemo- and regioselectivity due to the avoidance of the use of air- and moisture-sensitive organometallic reagents and stoichiometric metal reductants. Mechanistic studies suggested that the alkyl radical is generated via NiI species or photocatalyst.

Catalytic Asymmetric Barbier Reaction of Ketones with Unactivated Alkyl Electrophiles.

The Barbier reaction is a reductive-type addition of an aldehyde or ketone with an organic electrophile in the presence of a terminal metal reductant, providing a straightforward and efficient method for carbon-carbon bond formation. This reaction possesses the advantage of circumventing the preparation of moisture- and air-sensitive organometallic reagents. However, the catalytic Barbier reaction of ketones to construct tetrasubstituted stereogenic centers is largely underdeveloped, despite its great potential for accessing synthetically challenging chiral tertiary alcohol. Particularly, the leveraging of unactivated alkyl electrophiles as coupling components is still rarely exploited. Herein, we disclose a photoredox-assisted cobalt-catalyzed asymmetric alkylative Barbier-type addition reaction of ketones to address the aforementioned challenges, thereby allowing for the construction of highly congested tetrasubstituted carbon centers. The alkyl addition fragments could be either readily accessible unactivated alkyl halides or redox-active esters generated through a decarboxylative pathway. Both types of alkyl electrophiles include primary, secondary, and tertiary ones, thus affording diverse enantioenriched tertiary alcohols with a broad substrate scope. This enantioselective protocol is applied for the expedient synthesis of core structure of Sofdra, a very recent FDA-approved drug in 2024. The newly developed bisoxazolinephosphine (NPN) ligand enables high enantioselectivity in this asymmetric reductive addition process.

Corrosion of Copper, Cupronickel, Nickel Aluminium Bronze and Super-Duplex Stainless Steel Rotating Cylinder Electrodes in Seawater under Turbulent Flow Conditions

The corrosion of uncoated metals in a marine environment restricts the choice of suitable engineering metals and alloys. Anodic dissolution of metal and cathodic reduction of oxygen are important processes and formation of a surface oxide film can affect both electrode reactions. Charge transfer and mass transfer data can provide information on corrosion rate and mechanism. Several metals and alloys having a history of use in marine engineering are considered, including copper, two copper alloys (cupronickel and nickel aluminium bronze) plus a more recent addition to strong, corrosion resistant alloys (a super duplex stainless steel). The rotating cylinder electrode offers the benefits of a controlled, turbulent flow of electrolyte, facilitating controlled mass transfer in a compact cell geometry which is well-suited to bench-top operation. These features are illustrated using a variety of electrochemical techniques, including open-circuit potential vs time monitoring, linear sweep voltammetry, rotation speed step- or potential step current transients and linear polarisation resistance measurements. Seawater taken from Langstone Harbour, Hampshire, UK, was filtered, air-saturated, pH 8.0 and maintained at 25 °C. Dimensionless group correlations and graphical plots (using an analogous approach to the Koutecky-Levich equation for an RDE) enabled contributions of charge transfer-, mixed- and mass transfer- controlled data to be appreciated, allowing the Tafel slopes of electrode reactions, the diffusion coefficient of dissolved oxygen, the mass transfer coefficient for oxygen reduction and the mean corrosion rate to be estimated.

Composting as a Cleaner Production Strategy for the Soil Resource of Potato Crops in Choconta, Colombia

Choconta is the municipality in Colombia with the greatest prevalence of potato planting, representing 70.90% of the total territory. However, this crop has been affected by the presence of pests, diseases, and chemical contaminants from pesticides and chemical fertilizers that deteriorate the soil and, therefore, the quality of the final product. Compost (organic waste with specific characteristics and made from waste generated in Choconta) was studied as a sustainable production strategy to increase soil quality and thereby the quality of the local potato crop. For this purpose, a 3 × 2 experiment design was implemented with three treatments (0%, 25%, and 50% compost) and two variables (young potato and mature potato) in duplicate for 4 months. In this experiment, the use of compost led to an improved final product, which went from a floury texture to a dense and creamy texture. The use of compost also reduced the levels of heavy metals, such as lead, with a higher removal in treatment 3 (50% composting). The estimated direct cost of the composting process was USD 280.85, slightly lower than that of the application of fertilizers at USD 294.48. The use of fertilizers has a higher environmental impact due to the use of chemical products that have environmental and health implications. Using compost did not influence tuber harvest time but had a positive impact on tuber texture quality and on soil resources through the reduction in heavy metals, especially lead (16.40–18.03 ppm for treatment 1, 17.96–18.49 ppm for treatment 2, and 15.67–17.88 ppm for treatment 3). Using compost could be environmentally and economically beneficial for local farmers, and it promotes the circular economy and sustainable communities.

Manuscript number: ejic.202400523Isomerism in Phenyl 2‐Pyridyl Ketoxime Metal Complexes

The octahedral complex [RhCl2(ppkoH)(ppko)] (1) was obtained from the reaction between RhCl3 and phenyl 2‐pyridyl ketoxime (ppkoH). Attempts to prepare the corresponding octahedral platinum compound from K2PtCl6 gave instead the square planar [Pt2+(ppko)2] (2), but when the halogen was changed to bromine, the octahedral [Pt4+Br2(ppko)2] (3) was formed. The crystal structures were determined by X‐Ray crystallography. All the compounds have two N,N‐chelating oxime ligands. In 1, one of them is deprotonated, while in 2 and 3 both ligands are deprotonated. Compounds 1 and 3 have two halogen ligands in trans position. In 1 the oxime groups are situated mutually in cis position with an intramolecular hydrogen bond between the two N‐O(H) groups. The formation of 2 involves reduction of the platinum metal and the complex has oximes in trans position to each other. Compound 3 has an all‐trans geometry. Since octahedral and square planar compounds have a possibility to isomerism, we studied the relative stability of different geometries by DFT calculations. A mixture of isomers is likely to be formed in the reactions, but the most stable form was found to crystallize. The properties of the electron density in the preferred isomers were also investigated via QTAIM methods.

Enhanced Pollutant Removal and Antifouling in an Aerobic Ceramic Membrane Bioreactor with Bentonite for Pharmaceutical Wastewater Treatment.

This study examined the impact of adding bentonite clay (concentration of 1.5 to 10 g/L) to a pilot-scale aerobic ceramic membrane bioreactor (AeCMBR) for treating pharmaceutical wastewater (PhWW). The hydraulic retention time (HRT) was maintained at 24 h; the dissolved oxygen was between 2 mg/L (on) and 4 mg/L (off) throughout operation. Organic and nitrogen pollution removal rates and heavy metal (Cu, Ni, Pb, Zn) reduction rates were assessed. The chemical oxygen demand (COD) removal efficiency exceeded 82%. Adsorption improved ammonia (NH4+) removal to 78%; the addition of 5 g of bentonite resulted in a 38% improvement compared with the process without bentonite. The average nitrate concentration decreased from 169.69 mg/L to 43.72 mg/L. The average removal efficiencies for Cu, Ni, Pb and Zn were 86%, 68.52%, 46.90% and 56.76%, respectively. Bentonite at 5 g/L significantly reduced membrane fouling. The cost-benefit analysis enabled us to predict that the process will meet the multiple objectives of durability, treatment performance and economic viability. The combination of an AeCMBR and bentonite adsorption has proven to be a valuable solution for treating highly polluted wastewater.

Green integrative large scale treatment of tannery effluent, CO2 sequestration, and biofuel production using oleaginous green microalga Nannochloropsis oculata TSD05: An ecotechnological approach

In this present investigation, the freshwater microalga Nannochloropsis oculata TSD05 was used to demonstrate multiforius environmental applications viz., bioremediation of tannery effluent, carbon sequestration, and green renewable biodiesel production from treated microalgal biomass. The microalga Nannochloropsis oculata TSD05 was exhibited unique heavy metal reduction capabilities and reduced significant amount of heavy metals viz., 96.62% of copper (Cu2+), 99.9% of chromium (Cr3+), 98.36% of zinc (Zn2+), 98.71% of cadmium (Cd2+), 97.96% of lead (Pb2+), 98.88% of Cobalt (Co2+), and 98.76% of nickel (Ni2+). The biosorption capacity rate (qmax) of heavy metals reduction and highest R2 of 97.84% exhibited at 12 days of effluent treatment by Langmuir and Freundlich isotherm models. The phytotoxicity analysis was tested againt treated tannery effluent using Vigna radiate, Sapindus muukorossi seeds and 98.45%, 99.05% seeds were germinated. The Nannochloropsis oculata TSD05 microalga was utilized 98.45% of CO2 by biofixation kinetics, 372 mg g−1 of lipid, 3.65 mg mL−1 of biomass and 4.64 mLg−1 of biodiesel were produced. The produced biodiesel was confirmed and identification of 18 fatty acid methyl ester (biodiesel) compounds using GCMS. The recognition of 17 functional groups was identified using FTIR analysis and the microalga Nannochloropsis oculata TSD05 potential for sustainable and renewable green energy production. The potential future application of Nannochloropsis oculata TSD05 is to increase lipid production and biodiesel yield. Scaling up the bioremediation process can also validate these microalga's feasibility for use in wastewater treament. Enhancing heavy metal biosorption and carbon sequestration efficiency through genetic engineering could also maximize environmental benefits.

Catalytic Effect of Titanium Ions on the Cathodic Reduction of Selenium (VI), Copper (II), Uranium (VI) Ions and Other Metals in an Aqueous Solutions

It is known that catalytic processes are widely applied in the field of organic chemistry; however they also play a significant role in inorganic chemistry. Nonetheless, numerous unresolved issues persist in the technology of inorganic substances and the extraction of metals and nonmetals in their elemental states. This publication aims to consolidate the results of our pioneering research utilizing the redox Ti (IV)–Ti (III) system, which demonstrates a catalytic action on the cathodic reduction of selenium (VI), copper (II), platinum (IV), palladium (IV), bismuth, arsenic (V) ions, uranium (VI), as well as manganese dioxide suspension. It has been demonstrated that in the presence of the redox Ti (IV)–Ti (III) system, hard-to-reduce selenate ions can be reduced at room temperature. The catalytic action of the redox Ti (IV)–Ti (III) system has been reliably demonstrated, and the reaction mechanism has been established. In the electrochemical production of metal powders (Cu, Pt, Pd, Bi) at cathode current densities exceeding the limiting value, a portion of the current is irreversibly lost to the discharge of hydrogen ions. Consequently, the current efficiency (CE) for powder production does not exceed 80 %. We have established that in the presence of titanium (IV) ions, due to their catalytic action, the CE increases by more than 15 %. It has also been shown that during the cathodic polarization of hexavalent uranium its reduction to uranium (IV) in the presence of the catalyst increases by more than 50 %. The reduction of hard-to-reduce arsenate ions in the presence of titanium (IV) ions proceeds with high CE to the active trivalent state, and further reduction can proceed electrochemically. The cathodic reduction of a manganese dioxide suspension was investigated. In the presence of a catalyst — titanium (IV) ions, manganese in this dioxide is reduced to the divalent state with a current efficiency exceeding 90 %.

Efficiency of Canna indica, Phragmites australis and Eichhornia crassipes in Remediation of Leachate Through a Vertical Flow Constructed Wetland

Leachate treatment and disposal from landfills is one of major environment concern. Leachate contains various pollutants which may cause various environmental and health problem to terrestrial and aquatic living bodies. In the Present study, Landfill leachate was collected from Okhla landfill, New Delhi and treatment of leachate was done by using laboratory scale vertical flow treatment grown with Canna indica, Phragmites australis and Eichhornia crassipes, respectively. The experimental plots were obtained by set up of four different flow rates by balancing the inflow manipulations to obtain detention times of 1,7,14 for 21 days. The reduction of COD, BOD, NH4-N, TSS and heavy metals (Cd, Cu, Co, Cr, As, Pb, Ni, Fe, Zn and V) were investigated for 21 days. Average removal efficiency (%) for VCW (W1) planted with Canna indica showed 77.7%, 78.7%, 63.6%, and 76.7% for COD, BOD, NH4-N and TSS, respectively. Heavy metal removal (%) efficiencies of W1 planted with Canna indica was 60%, 82.5%, 100%, 29.37%, 27.9%, 62.67%, 13.33%, 44.5%, 75.2% and 78.85% for As, Cr, Cd, Cu, Co, Fe, Mn, Pb, Zn and V, in given order. VCW(W2) planted with Eicchornia crassipes species has shown reduction efficiency (%) of COD (68.5%), BOD (52%), NH4-N (45.4%), TSS (92.75%), respectively and in case of heavy metal 89.9% Cr, 100% Cd, 53.49% Cu, 62.7% Co, 85.2% Fe, 67.9% Ni, 76.2% Pb, 83.08% Zn, 65% As and 61.15% V, respectively. VCW (W3) planted with Phragmites australis exhibited removal efficiency (%) of COD (68.5%), BOD (52%), NH4-N (45.4%) and TSS (92.7%), respectively. Phragmites australis was able to remove As (100%), Cd (100%), Cr (89.9%), Cu (53.49%), Co (62.7%), Fe (85.82%), Ni (67.9%), Pb (76.2%), V (61.15%) and Zn (83.08%), respectively. All the three species were able to remove Cd (100 %). However, Canna indica (W1) has highest removal efficiencies (%) of COD (77.7%), BOD (78.7%) and NH4-N (63.6 %), respectively. Eicchornia crassipes has highest reduction efficiency (%) of TSS (92.75%), Cr (89.9%), Cd (100%), Cu (53.49%), Co (62.7%), Fe (85.2%), Ni (67.9%), Pb (76.2%) and Zn (83.08%), respectively. Phragmites australis was found good for removal of As (100 %) and Cd (100%). The result highlighted that these plant species can be used as single in lab scale Constructed wetland for the treatment Organic pollutants and heavy metals from landfill leachate.

Molecular Dynamics Simulation Model of Alkali Metal Reduction of Gaseous Halides and Reaction Mechanism Analysis.

The reaction of gaseous hydrogen halides with alkali metals provides a new pathway for producing hydrogen. The structure and reactivity of alkali metals are crucial for the reduction of gaseous halides. However, traditional gas-phase reaction models fail to provide insights into the dynamic processes occurring during alkali metal reactions. In this paper, based on the reaction between Hydrogen fluoride (HF) and alkali metal sodium (Na), we have established a metallic Na slab. HF molecules were randomly inserted above the surface of the Na slab, creating a reaction model for the reduction of HF by metallic Na. The reaction of HF on the Na surface was calculated using first-principles molecular dynamics. The configuration and reaction of the Na surface and HF molecules at different times were judged by analyzing the radial distribution function and mean squared displacement. Na atoms reacted with HF to produce intermediate NaFH, and then the F-H bond broke to form NaF and H. The F-H bond breaking of intermediate NaFH was the key step, and the kinetic parameters of this key step were calculated.

Modular Synthesis of Heterobenzylic Amines via Carbonyl Azinylative Amination

AbstractTransformations enabling the synthesis of α‐alkyl, α′‐2‐azinyl amines by addition of 2‐heteroaryl‐based nucleophiles to in situ‐generated and non‐activated alkyl‐substituted iminium ions are extremely rare. Approaches involving classical 2‐azinyl organometallics, such as the corresponding Grignard reagents, often fail to produce the desired products. Here, we report an operationally straightforward solution to this problem through the development of a multicomponent coupling process wherein a soft 2‐azinyl indium nucleophile, generated in situ from the corresponding 2‐iodo heteroarene and indium powder, adds to an iminium ion that is also formed directly in the reaction. This modular carbonyl azinylative amination (CAzA) displays a broad scope and only a metal reductant is needed to generate a reactive 2‐azinyl nucleophile. Beyond the addition to iminium ions, the 2‐azinyl addition to polyfluoromethyl ketones forms the corresponding tertiary alcohols. Together, the products of these reactions possess a high degree of functionality, are typically challenging to synthesize by other methods, and contain motifs recognized as privileged in the context of pharmaceuticals and agrochemicals.

Insights into transition metal encapsulated inside carbon aerogel for accelerated electro-peroxone oxidation: Activity evaluation and reactive oxygen species generation

Transition metals have critical influences on the generation of reactive oxygen species in activating O3 and H2O2, as the binary oxidant sources in electro-peroxone (EP). To evaluate the catalytic activity of different metals and reveal the reactive oxygen species generation in heterogeneous EP, series of metals encapsulated inside carbon aerogel spheres (M@CS, M=Fe, Co, Ni, Zn) were fabricated for strengthening EP. Atrazine was used as model pollutant due to its low reactivity with O3, and the abatement trends followed Co@CS > Fe@CS > Ni@CS > Zn@CS. Co@CS exhibited the superior catalytic activity with maximum metal active site utilization (1.28 × 103 min-1 mol-1 per mole Co atom sites at pH 7) and minimum electric energy consumption (0.106 kWh/m3-log). The catalytic activity of M@CS was related to the adsorption energies for O3 and H2O2 (Fe@CS > Co@CS > Ni@CS > Zn@CS) and the graphitization degree (Co@CS > Fe@CS > Ni@CS > Zn@CS). Verified by theoretical calculation and in-situ Fourier transformed infrared, the metal effectively promoted the adsorption and decomposition of O3 and H2O2 into the surface oxygen intermediates, finally generating ·OH/·O2-/1O2. The carbon layer was conducive to the reduction of internal metal, ensuring catalyst durability. Electronic paramagnetic resonance and kinetic model revealed the occurrence, ratio and transient concentration of ·OH/·O2-/1O2 in M@CS/EP. M@CS/EP showed good performance for pollutant removal in coexistence of anions, humic acid and real water. This study provides guidance for selecting the metal–carbon catalyst in heterogeneous EP.

Electrochemically Driven Nickel-Catalyzed Enantioselective Hydro-Arylation/Alkenylation of Enones.

Herein, the study reports the first electrochemical nickel-catalyzed enantioselective hydro-arylation/alkenylation of enones in an undivided cell with low-cost electrodes in the absence of external reductants and supporting electrolytes. Aryl bromides/iodides/triflates or alkenyl bromides are employed as electrophiles for the efficient preparation of more than 56 valuable β-arylated/alkenylated ketones in a simple manner (up to 97% yield, 97% ee). With the advantages of electrochemistry, excellent functional group tolerance and late-stage modification of complex natural products and pharmaceuticals made the established protocol greener and more economic. Mechanism investigation suggests that a NiI/NiIII cycle may be involved in this electro-reductive reaction rather than metal reductant driven Ni0/NiII cycle. Overall, the efficient electrochemical activation and turnover of the nickel catalyst avoid the drawbacks posed by the employment of stoichiometric amount of sensitive metal powder reductants.