Electronic Effects Research Articles

Unraveling the effect and difference of S or Si atoms modified Pd-based catalysts in tuning catalytic performance of C2H2 semi-hydrogenation

Modifying the spatial scale of active site has been proven a good strategy for enhancing catalytic performance. In this study, the Pd-based catalysts with different spatial scale of active site were constructed via the modification of non-metallic S or Si atoms over Pd, Cu alloyed Pd SACs, PdAg surface alloy and PdM (M=Au, Ag) IMCs catalysts, then, C2H2 semi-hydrogenation catalytic performance was identified based on DFT calculations. The findings indicate that the catalytic performance of C2H2 semi-hydrogenation is greatly influenced by the spatial extent of active site and the electronic effect modified by the S or Si atoms. Geometric effect caused by S or Si atoms reduces the spatial scale of active site over S/Pd-2 × 2, Si/Pd-3 × 3, S/Pd6Ag, S/Pd1Au1, S/Pd1Ag1 and Si/Pd1Ag1, thereby preventing green oil generation. Electronic effect caused by S or Si atoms leads to far away from the Fermi level of d-band center over S/Pd-2 × 2, Si/Pd-3 × 3, S/Pd1Au1, S/Pd1Ag1 and Si/Pd1Ag1 to improve C2H4 production activity and selectivity. Seven catalysts S/Pd-2 × 2, Si/Pd-3 × 3, PdCu-2 × 2, S/Pd6Ag, S/Pd1Au1, S/Pd1Ag1 and Si/Pd1Ag1 are screened out to present high selectivity and activity of C2H4 production, and effectively prevent green oil generation. This study provides valuable structural insights for designing high-performance catalysts by the modification of non-metallic atom in C2H2 semi-hydrogenation.

Construction of molecular semiconductor traps to improve the energy storage performance of novel cyanopolynorbornene

To meet the demand of film capacitors in harsh condition applications, research workers devote their effort to develop high temperature resistant polymer dielectrics with high energy density. In this paper, a new type of dipole glass polymer, polynorbornene containing cyano-group side chain (PDMBN) is prepared by ring opening metathesis polymerization. The high dipole moment of the cyano-group possesses high polarization, resulting in that the discharge energy density (Ud) of 8.6 J/cm3 and efficiency of 84 % are found in the PDMBN at room temperature. Via using three organic semiconductors with increased electron affinity (NBTI, NBTI-SO2 and NBTI-2SO2) as the fillers, the energy storage properties of PDMBN matrix are further improved due to the binding effect of free electrons. In addition, the interfacial barrier height is inversely proportional to the temperature, electric field and electron affinity of fillers. As a result, 0.7- wt% NBTI-SO2/PDMBN achieves a maximal Ud of 11.6 J/cm3 at 600 MV/m and room temperature. At elevated temperatures, the conduction loss of polymer PDMBN increases sharply, causing a rapid decline in energy storage performance. Nevertheless, the maximum Ud of 0.7-wt%NBTI/PDMBN composite film at 100 °C and 150 °C can reach 6.2 J/cm3 and 4.5 J/cm3, respectively. This study is helpful for the design of polynorbornene dielectrics, and provides an important reference for the construction of carrier traps in polymer dielectrics at high temperature.

Metabolic characteristic profiling of 1-amino-3,3-dimethyl-1-oxobutan-2-yl-derived indole and indazole synthetic cannabinoids in vitro

Characterizing the metabolic profiles of synthetic cannabinoids (SCs), a type of new psychoactive substances, is of particular importance for forensic detection and analysis. Although the metabolism of individual SCs derived from 1-amino-3,3-dimethyl-1-oxobutan-2-yl (ADB-SCs) has been reported, their metabolites also undergo a continuous change and combination of their tail and core regions. Therefore, elucidating the metabolic characteristics and effects of these structures is essential to enhance our understanding. In this study, the human liver microsome was used as the model for studying the in vitro phase I metabolism of 12 ADB-SCs, and the metabolites obtained were analyzed using ultra-high performance liquid chromatography–tandem four-level rod-electrostatic field orbital ion trap mass spectrometry to determine type, structure, and relative contents. The results indicated that hydroxylation and N-dealkylation were the major metabolic pathways in 12 ADB-SCs. The effects of the core and tail on the metabolism of these ADB-SCs were studied using theoretical calculations. For N-dealkylation metabolism, the strong electron-withdrawing conjugative effect of the –N= moiety in the pyrazole ring, steric hindrance of the tail, and electronic effect of substituents on the tail significantly affected metabolism. Further, it changed the relative contents of N-dealkylation metabolites. For hydroxylation, the reaction types were inconsistent at different parts. For instance, the phenyl group of the core is electrophilic, and its electron cloud density determines whether the phenyl group can be hydroxylated at the specific metabolic sites. Meanwhile, hydroxylation of the neopentyl moiety of the linked group involves the oxidation of aliphatic C–H bonds, whereas amide–hydroxylamine tautomerism affects hydroxylation metabolism. When the alkyl chain in the tail contains functional groups (such as –F and >CC<), oxidative defluorination or dihydrodiol metabolites are produced. Taken together, we systematically determined d the effect of functional groups in the core and tail of ADB-SCs on their metabolism, validating confirmed the feasibility of ADB-SC metabolism prediction based on their structural characteristics.

High-Voltage Single-Ion Covalent Organic Framework Electrolytes Enabled by Nitrile Migration Ladders for Lithium Metal Batteries.

The poor electrochemical stability window and low ionic conductivity in solid-state electrolytes hinder the development of safe, high-voltage, and energy-dense lithium metal batteries. Herein, taking advantage of the unique electronic effect of nitrile groups, we designed a novel azanide-based single-ion covalent organic framework (CN-iCOF) structure that possesses effective Li+ transport and high-voltage stability in lithium metal batteries. Density functional theory (DFT) calculations and molecular dynamics (MD) revealed that electron-withdrawing nitrile groups not only resulted in an ultralow HOMO energy orbital but also enhanced Li+ dissociation through charge delocalization, leading to a high tLi+ of 0.93 and remarkable oxidative stability up to 5.6 V (vs. Li+/Li) simultaneously. Moreover, cyanation leveraging Strecker reaction transformed reversible imine-linkage to a stable sp3-carbon-containing azanide anion, which facilitated contorted alignment of transport "ladders" along the one-dimensional anionic channels and the ionic conductivity could reach 1.33×10-5 S cm-1 at ambient temperature without any additives. As a result, CN-iCOF allowed operation of solid-state lithium metal batteries with high-voltage cathodes such as LiNi0.8Mn0.1Co0.1O2 (NCM811), demonstrating stable lithium deposition up to 1,100 h and reversible battery cycling at ambient temperature up to 4.5 V, shedding light on the importance of discovering new functionality for forthcoming high-performance batteries.

Insights into One-Dimensional Thermoelectric Materials: A Concise Review of Nanowires and Nanotubes.

This brief review covers the thermoelectric properties of one-dimensional materials, such as nanowires and nanotubes. The highly localised peaks of the electronic density of states near the Fermi levels of these nanostructured materials improve the Seebeck coefficient. Moreover, quantum confinement leads to discrete energy levels and a modified density of states, potentially enhancing electrical conductivity. These electronic effects, coupled with the dominance of Umklapp phonon scattering, which reduces thermal conductivity in one-dimensional materials, can achieve unprecedented thermoelectric efficiency not seen in two-dimensional or bulk materials. Notable advancements include carbon and silicon nanotubes and Bi3Te2, Bi, ZnO, SiC, and Si1-xGex nanowires with significantly reduced thermal conductivity and increased ZT. In all these nanowires and nanotubes, efficiency is explored as a function of the diameter. Among these nanomaterials, carbon nanotubes offer mechanical flexibility and improved thermoelectric performance. Although carbon nanotubes theoretically have high thermal conductivity, the improvement of their Seebeck coefficient due to their low-dimensional structure can compensate for it. Regarding flexibility, economic criteria, ease of fabrication, and weight, carbon nanotubes could be a promising candidate for thermoelectric power generation.

Structural evolution of cobalt for the production of long-chain paraffins by CO2 hydrogenation

A new role of alkali metals in the direct hydrogenation of CO2 to C5+ species over Co catalysts was proposed. During the CO2 hydrogenation, Na-promotion encouraged a new structural evolution (i.e., a thin oxygen vacancy (Ov)-rich Co3O4/Co2C shell and a Co0 core). This facilitated the migration of CHxO and CO species produced at the shell to the adjacent Co2C shell and Co0 core, where they undergo further chain growth. In contrast, Li- and K-promotion resulted in the generation of a thick and Ov-poor Co3O4 shell without Co2C, while in the absence of alkali metal promotion, Co0 was exposed as the outmost surface; in both the cases, methanation dominated. The ability of Na-promotion to remove –OH* from the Co surface helped maintain the thickness and valance state of the Co oxide shell. Thus, the Na-promotion developed the chain growth and CO producing core–shell structure, rather than any electronic promotional effects.

Gyrokinetic simulations of the kinetic electron effects on the electrostatic instabilities on the ITER baseline scenario

The linear and nonlinear simulations are carried out using the gyrokinetic code NLT for the electrostatic instabilities in the core region of a deuterium plasma based on the International Thermonuclear Experimental Reactor (ITER) baseline scenario. The kinetic electron effects on the linear frequency and nonlinear transport are studied by adopting the adiabatic electron model and the fully drift-kinetic electron model in the NLT code, respectively. The linear simulations focus on the dependence of linear frequency on the plasma parameters, such as the ion and electron temperature gradients , the density gradient and the ion–electron temperature ratio . Here, is the major radius, and and denote the electron and ion temperatures, respectively. is the gradient scale length, with denoting the density, the ion and electron temperatures, respectively. In the kinetic electron model, the ion temperature gradient (ITG) instability and the trapped electron mode (TEM) dominate in the small and large region, respectively, where is the poloidal wavenumber. The TEM-dominant region becomes wider by increasing (decreasing) ( ) or by decreasing . For the nominal parameters of the ITER baseline scenario, the maximum growth rate of dominant ITG instability in the kinetic electron model is about three times larger than that in the adiabatic electron model. The normalized linear frequency depends on the value of , rather than the value of or , in both the adiabatic and kinetic electron models. The nonlinear simulation results show that the ion heat diffusivity in the kinetic electron model is quite a lot larger than that in the adiabatic electron model, the radial structure is finer and the time oscillation is more rapid. In addition, the magnitude of the fluctuated potential at the saturated stage peaks in the ITG-dominated region, and contributions from the TEM (dominating in the higher region) to the nonlinear transport can be neglected. In the adiabatic electron model, the zonal radial electric field is found to be mainly driven by the turbulent energy flux, and the contribution of turbulent poloidal Reynolds stress is quite small due to the toroidal shielding effect. However, in the kinetic electron model, the turbulent energy flux is not strong enough to drive the zonal radial electric field in the nonlinear saturated stage. The kinetic electron effects on the mechanism of the turbulence-driven zonal radial electric field should be further investigated.

Ketalization mechanism of glycerol to biobased glycerol levulinate ketal over HZSM-5: A combined experimental and theoretical study

Methyl levulinate ketal (MLK) is a novel biobased chemical derived from glycerol via ketalization, and exploring its synthesis mechanism is of great significance for the high-value utilization of biomass resources. In this study, the ketalization reaction of glycerol was evaluated using the MLK yield calculated by the GC internal standard method. The acidity of HZSM-5 was determined by NH3-TPD. The catalyst screening experiments demonstrated that HZSM-5 in zeolites and AlCl3 in metal salts exhibited high catalytic activity in the synthesis of MLK. Furthermore, the kinetic results indicated that the HZSM-5 zeolite catalyst exhibited a lower apparent activation energy in catalyzing the synthesis of MLK compared to the metal salt catalyst AlCl3. The ketalization reactions of levulinate and glycerol catalyzed by different types of acidic sites in HZSM-5 were then investigated using the density functional theory method. A comprehensive catalytic path, free energy changes, intermediates, and transition state structures were proposed. Furthermore, the free energy barriers of ethyl levulinate ketal and butyl levulinate ketal catalyzed by HZSM-5 were calculated, and the difference between the steric hindrance effect and the electronic effect of alkyl in levulinate was compared. This study enhances the understanding of ketalization reactions and will be useful in future catalyst design studies.

Coupling interface, electronic and conjugation effects in C-COFs/TiO2 composite structure toward boosting photocatalytic hydrogen evolution

Hydrogen energy, recognized as a pivotal clean energy source, has attracted considerable attention in the realm of photocatalytic hydrogen production. Nevertheless, inorganic materials were difficult to regulate band gaps, resulting in limited photogenerated carrier rates. Additionally, organic materials frequently suffer from insufficient stability and a propensity for electron recombination. Therefore, fully utilizing the interface effect will become an important breakthrough for novel and efficient catalysts. Herein, hydroxylate covalent organic frameworks (H-COFs) were formed by direct synthesis method, in addition, titanium dioxide (TiO2) was used as an inorganic substrate, and TiO2 was transformed titanium acid under weakly acidic conditions, meanwhile, chloride covalent organic frameworks (C-COFs) growth on TiO2 surface by interface effect when H-COFs were formed into C-COFs under titanium acid. The structure characteristics, photoelectric performance, bandgap width and stability of C-COFs/TiO2 were confirmed through characterization analysis. C-COFs/TiO2 exhibit strong stability, conjugation effects, electron deficiency effects, and catalytic efficiency. Hydrogen production rate up to 5598 μmol g−1 h−1 by C-COFs/TiO2 as photocatalyst. C-COFs/TiO2 lead to 161 times improvement in photocatalytic activity for TiO2 and 3.6 times improvement in photocatalytic activity for H-COFs. The catalytic reaction mechanism was obtained by utilizing experimental data and DFT calculation. This synergistic integration of organic inorganic combined catalyst provides a foundational framework for advancing research into novel photocatalysts.

Electronic and Molecular Structures of a Series of Nickel Bis-1,1-Dithiolates.

A series of homoleptic Ni bis-1,1-dithiolates, [Ni(S2C2RR')2]2- (R=CN, R'=CN, CO2Et, CONH2, Ph, Ph-4-Cl, Ph-4-OMe, Ph-4-NO2, Ph-3-CF3, Ph-4-CF3, Ph-4-CN; R=NO2, R'=H; R=R'=CO2Et) have been synthesized from the reaction of the alkali metal salt of the ligand and nickel chloride, and isolated as tetraphenylphosphonium or tetrabutylammonium salts. The complexes were characterized by X-ray crystallography, high-resolution mass spectrometry, and infrared (IR), nuclear magnetic resonance (NMR) and electronic absorption spectroscopies. The molecular structures show a rigidly square planar Ni(II) center linking two four-membered chelate rings whose dimensions are constant across the series. The electronic effect of the ligand substituent is revealed in the 13C NMR and electronic spectra, and corroborated by density functional calculations. Electron withdrawing groups deshield the low-field CS2 resonance, and the signature charge transfer band in the visible region is red-shifted. These observables have been accurately reproduced computationally, and revealed the Ni contribution to the ground state diminishes with decreasing electron withdrawing capacity of the ligand substituent. In contrast to 1,2-dithiolates, the redox inactivity afforded by 1,1-dithiolates stems from the smaller chelate ring and substantially reduced sulfur content that is key to stabilizing the radical form.

Diffusing on Two Levels and Optimizing for Multiple Properties: A Novel Approach to Generating Molecules with Desirable Properties.

In the past decade, Artificial Intelligence (AI) driven drug design and discovery has been a hot research topic in the AI area, where an important branch is molecule generation by generative models, from GAN-based models and VAE-based models to the latest diffusion-based models. However, most existing models pursue mainly the basic properties like validity and uniqueness of the generated molecules, a few go further to explicitly optimize one single important molecular property (e.g., QED or PlogP), which makes most generated molecules little usefulness in practice. In this paper, we present a novel approach to generating molecules with desirable properties, which expands the diffusion model framework with multiple innovative designs. The novelty is two-fold. On the one hand, considering that the structures of molecules are complex and diverse, and molecular properties are usually determined by some substructures (e.g., pharmacophores), we propose to perform diffusion on two structural levels: molecules and molecular fragments respectively, with which a mixed Gaussian distribution is obtained for the reverse diffusion process. To get desirable molecular fragments, we develop a novel electronic effect based fragmentation method. On the other hand, we introduce two ways to explicitly optimize multiple molecular properties under the diffusion model framework. First, as potential drug molecules must be chemically valid, we optimize molecular validity by an energy-guidance function. Second, since potential drug molecules should be desirable in various properties, we employ a multi-objective mechanism to optimize multiple molecular properties simultaneously. Extensive experiments with two benchmark datasets QM9 and ZINC250k show that the molecules generated by our proposed method have better validity, uniqueness, novelty, Fr´echet ChemNet Distance (FCD), QED, and PlogP than those generated by current SOTA models. The Code of D2L-OMP is available at https://github.com/bz99bz/D2L-OMP.

Electrohydrodynamic-Jet-Printed SnO2-TiO2-Composite-Based Microelectromechanical Systems Sensor with Enhanced Ethanol Detection.

Ethanol sensors have found extensive applications across various industries, including the chemical, environmental, transportation, and healthcare sectors. With increasing demands for enhanced performance and reduced energy consumption, there is a growing need for developing new ethanol sensors. Micro-electromechanical system (MEMS) devices offer promising prospects in gas sensor applications due to their compact size, low power requirements, and seamless integration capabilities. In this study, SnO2-TiO2 nanocomposites with varying molar ratios of SnO2 and TiO2 were synthesized via ball milling and then printed on MEMS chips for ethanol sensing using electrohydrodynamic (EHD) printing. The study indicates that the two metal oxides dispersed evenly, resulting in a well-formed gas-sensitive film. The SnO2-TiO2 composite exhibits the best performance at a molar ratio of 1:1, with a response value of 25.6 to 50 ppm ethanol at 288 °C. This value is 7.2 times and 1.8 times higher than that of single SnO2 and TiO2 gas sensors, respectively. The enhanced gas sensitivity can be attributed to the increased surface reactive oxygen species and optimized material resistance resulting from the chemical and electronic effects of the composite.

Exploring the key role of electronic effects in Pd catalysts supported on Ni-modified N-doped porous carbon for direct synthesis of H2O2 under atmospheric pressure

Developing high-performance catalysts for direct synthesis of hydrogen peroxide (H2O2; DSHP) remains challenging. The paper proposes a strategy to optimize Pd catalysts by enriching Ni-modified N-doped porous carbon. The theoretical studies indicate that Ni modulates the electronic structure of Pd through charge transfer and strain effects, effectively reducing the adsorption energy of reaction intermediates. Furthermore, the Crystal Orbital Hamilton Population (COHP) analysis demonstrated that the energy-integrated COHP (ICOHP) of the OO bonds in O2* (* denotes the adsorbed state), OOH*, and HOOH* were positively correlated with dissociation activation energies and negatively correlated with hydrogenation activation energies. The modulation of the electronic structure of Pd by Ni reduces the hydrogenation activation energies of O2* and OOH* and increases the dissociation activation energies of O2*, OOH*, and HOOH*, thereby enhancing the selectivity and productivity of H2O2. The experimental results aligned with the theoretical predictions, showcasing that the optimized Pd-Ni7.5/NPCs catalyst exhibited remarkable H2O2 selectivity and productivity of 70.5 % and 230.31 mol kgcat-1·h-1, respectively, surpassing the performance of Pd/NPCs (47.1 % and 52.3 mol kgcat-1·h-1). This study offers profound insights into the crucial role of electron effects in DSHP using nickel-modified palladium catalysts, providing strong evidence into the design and optimization of Pd catalysts.

From Proteome to Potential Drugs: Integration of Subtractive Proteomics and Ensemble Docking for Drug Repurposing against Pseudomonas aeruginosa RND Superfamily Proteins.

Pseudomonas aeruginosa (P. aeruginosa) poses a significant threat as a nosocomial pathogen due to its robust resistance mechanisms and virulence factors. This study integrates subtractive proteomics and ensemble docking to identify and characterize essential proteins in P. aeruginosa, aiming to discover therapeutic targets and repurpose commercial existing drugs. Using subtractive proteomics, we refined the dataset to discard redundant proteins and minimize potential cross-interactions with human proteins and the microbiome proteins. We identified 12 key proteins, including a histidine kinase and members of the RND efflux pump family, known for their roles in antibiotic resistance, virulence, and antigenicity. Predictive modeling of the three-dimensional structures of these RND proteins and subsequent molecular ensemble-docking simulations led to the identification of MK-3207, R-428, and Suramin as promising inhibitor candidates. These compounds demonstrated high binding affinities and effective inhibition across multiple metrics. Further refinement using non-covalent interaction index methods provided deeper insights into the electronic effects in protein-ligand interactions, with Suramin exhibiting superior binding energies, suggesting its broad-spectrum inhibitory potential. Our findings confirm the critical role of RND efflux pumps in antibiotic resistance and suggest that MK-3207, R-428, and Suramin could be effectively repurposed to target these proteins. This approach highlights the potential of drug repurposing as a viable strategy to combat P. aeruginosa infections.

Quaternary Cu2ZnSnS4 and Cu2ZnSnS4-WS2 composite for enhanced antioxidant, antibacterial, and photocatalyst for degradation of sulfamethoxazole

Antibiotic contamination possesses several adverse effects including antibiotic resistance, ecological impact, and human health concern etc. Hence there is need to find ways in mitigation of this environmental issue. In this study, Cu2ZnSnS4 (CZTS) nanoparticles (NPs) and CZTS-WS2 composite were synthesized and explored its photocatalytic efficiency in degrading sulfamethoxazole, an antibiotic. In addition, the antioxidant and antibacterial capabilities of CZTS NPs and CZTS-WS2 composites were also investigated. The CZTS NPs and CZTS-WS2 composites were synthesized by a modified hydrothermal method, and the physical properties were explored. The p-type pristine CZTS NPs semiconductor with a direct bandgap (1.49–1.51 eV) is non-toxic and has a remarkable photostability making it extremely valuable in light-harvesting and photocatalyst applications. Quaternary CZTS NPs loaded with 10 % WS2 exhibits good photocatalytic activity for the breakdown of sulfamethoxazole. The Fenton procedure was used to extract sulfamethoxazole from an aqueous solution. When compared to CZTS NPs (0.088 min−1), the apparent rate constant for CZTS-WS2 composite (0.223 min−1) is almost two and a half times higher. Reactive quenching studies showed that OH, O2−, and 1O2 all contributed to SMX deterioration, with 1O2 outperforming O2− and OH. An SMX transformation pathway in the CZTS-WS2 composite process was postulated based on the identified intermediates by LC/MS. Finally, the composite’s reusability and stability were assessed during five separate runs. CZTS-WS2 composite demonstrated more than 80 % radical scavenging efficiency. CZTS NPs and CZTS-WS2 composite also demonstrate antibacterial capabilities against E. coli, S. aureus, M. luteus, and C. albicans. This is the first paper on the photocatalytic study of the degradation of sulfamethoxazole using CZTS NPs and CZTS-WS2 composite as catalysts. The current CZTS-WS2 composite’s outstanding catalytic efficacy in the absence of severe oxidizing/reducing agents and pricey noble metals has been ascribed to its size, surface area, and electronic effect. Hence this work describes a novel approach to developing efficient materials for antioxidant, antibacterial, and photocatalysts for the degradation of sulfamethoxazole.

Direct Effect of Fast Electrons on Hexafluoroacetylacetone

Direct Effect of Fast Electrons on Hexafluoroacetylacetone

Oxygen concentration regulated the efficient liquefaction of vulcanized natural rubber

Oxidative liquefaction represents a promising avenue for the homogeneous and high-value utilization of waste tire rubber. Given that truck tires predominantly comprise natural rubber (NR), this study investigated the efficient liquefaction of vulcanized NR regulated by oxygen concentration. Remarkably, the liquefaction of vulcanized NR was realized with an oxygen concentration of 75 % at 200 °C within 3 min. FTIR spectroscopy showed that carbonyl, ether and sulphoxide groups were produced during the liquification of NR vulcanizates. Oxygen concentration significantly affected the oxidative efficiency of both the main chains and crosslinks, with a more pronounced effect observed on the main chains. Nevertheless, the similar molecular weights and polydispersity indices across various degraded products suggested a selective oxidative cleavage of the NR backbone. Furthermore, online ATR-FTIR was used to monitor the dynamic changes of NR's molecular structure to elucidate the oxidative degradation mechanism. The oxidative cleavage of NR main chain primarily occurred at the C-C bonds connected with allyl groups, producing oxidized products enriched with conjugated carbonyl groups. Alternatively, the main chain scission may also occur due to the electronic rearrangement effect of the C=C bond and produce saturated carbonyl groups. Oxygen concentration modulated the degradation efficiency of vulcanized NR, which provided an efficient strategy for the upcycling of NR-based waste tires.

Unraveling the Mechanism of Hydrogen Atom Transfer by a Nickel-Hypochlorite Species and the Influence of Electronic Effects.

The oxidation of hydrocarbons is an important chemical transformation with relevance to biology and industry. Ni-catalyzed transformations are more scarce compared to Mn or Fe but have gained attention in recent years, affording efficient oxidations. Understanding the mechanism of action of these catalysts, including the detection and characterization of the active nickel-oxygen species, is of interest to design better catalysts. In this work, we undertake a theoretical study to unravel the mechanism of formation of the previously reported [Ni(OCl)(HL)]+ (H2) and how it activates C-H bonds. We disclose that the active species is indeed compound [Ni(O)(HL)]+, formed after homolytic cleavage of the O-Cl bond in H2 assisted by a chlorine radical. [Ni(O)(HL)]+ mediates C-H activation through an asynchronous concerted mechanism, in which the transition state is given by hydrogen atom transfer. Moreover, the electronic tuning of the ligand has a very modest impact on the stability and reactivity of the corresponding X2 species. Effective oxidation state analysis reveals an intriguing electronic structure of H2 and [Ni(O)(HL)]+, in which both the macrocycic HL ligand and the OCl and O ligands behave as redox noninnocent. Such redox activity leads to a fully ambiguous oxidation state assignation.

Density functional theory study on frustrated Lewis pairs catalyzed C‐H activation of heteroarenes: Mechanism variation tuning by electronic effect

AbstractUnreactive C‐H bond activation is a new horizon for frustrated Lewis pairs (FLPs) chemistry. Although concerted mechanism (Science 2015, 349, 513) and stepwise carbene mechanism (Org. Lett. 2018, 20, 1102) have been proposed for the FLPs catalyzed C‐H bond activation of 1‐methylpyrrole, the influence of electronic properties of FLPs on the reaction mechanism is far away from well‐understood. In this study, an assortment of P‐B type FLPs with different electronic characteristic was employed to study the catalyzed C‐H bond activation of 1‐methylpyrrole by using density functional theory calculations. Detailed calculations demonstrated that the reactivity variation and the reaction mechanism binary of FLPs catalyzed C‐H activation can be varied by tuning electronic effect of Lewis base center. On the one hand, the concerted C‐H activation reactivity is mainly controlled by the electron donation of the lone pair of Lewis base center; thus, the FLPs with electron‐donating substituents (FLP1, FLP2, and FLP3) catalyzed the C‐H bond activation through concerted mechanism. On the other hand, the reactivity of stepwise carbene mechanism is mostly attributed to the vacant orbital of Lewis acid center; as a result, the FLP5 bearing ‐P(C6F5)2 preferred to catalyzed the bond activation through concerted mechanism. In contrast, a metathesis mechanism through strained four‐membered ring transition state is less feasible. These results should provide deeper insight and broader perspective to understand the structure and function of FLPs for rational design of FLPs catalyzed C‐H bond activation.

Palladium‐Catalyzed Isocyanide Insertion into the Remotely Activated N−H bond of 3‐(Phenylhydrazono)oxindoles: Facile Access to Indole‐N‐Carboxamide Derivatives

AbstractA convenient approach for synthesizing indole‐N‐carboxamide derivatives through palladium‐catalyzed isocyanide insertion into the N−H bond of 3‐(phenylhydrazono)oxindoles has been developed. The inclusion of the 3‐phenylhydrazone group proved essential in remotely activating the N−H bond of the oxindole. Also, it has been established that the reaction outcome is highly dependent on the electronic effects of the substituents.