Enhanced Electrocatalytic Activity of Methanol and Ethanol Oxidation in Alkaline Medium at Bimetallic Nanoparticles Electrochemically Decorated Fullerene-C60 Nanocomposite Electrocatalyst: An Efficient Anode Material for Alcohol Fuel Cell Applications

Direct alcohol fuel cells (DAFCs) have been recently playing a pivotal role in electrochemical energy sources and portable electronics. Research in DAFCs has proceeded to engage major attention due to their high catalytic activity, long-term stability, portability, and low cost. Herein, we present a facile surfactant-free route to anchor bimetallic Pd−W nanoparticles supported fullerene-C₆₀ catalyst (Pd-W@Fullerene-C₆₀) for high-performance electrooxidation of alcohols (methanol & ethanol) for DAFCs applications. Structural, elemental composition, and morphological analysis of the proposed catalyst were carried out using UV-Vis spectroscopy, X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM) and energy-dispersive x-ray spectroscopy (EDX). Electrochemical properties such as electrochemical activity, electrochemical active surface area (ECSA), and long-term stability of the Pd-W@Fullerene-C₆₀ catalyst for ethanol and methanol oxidation in the alkaline medium were explored by using cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and chronoamperometry (CA). Results revealed that the proposed catalyst showed enlarged ECSA, tremendous electrocatalytic activity, high poison tolerance limit, good reproducibility, and enhanced long-term stability as compared to the monometallic catalyst and commercially available catalyst (Pt/C) towards ethanol and methanol oxidation reaction. This enhanced potentiality of the Pd-W@Fullerene-C₆₀ catalyst is due to the synergistic effect of W−Pd nanoparticles and excellent electron kinetic from fullerene support material. These findings strongly suggest the Pd-W@Fullerene-C₆₀ catalyst as potential anode material for the alcohol oxidation reaction.     

Ruthenium (II) Catalyzed C(sp2)−H Bond Alkenylation of 2-Arylbenzo[d]oxazole and 2-Arylbenzo[d]thiazole with Unactivated Olefins

Functionalization of the bio-relevant heterocycles 2-arylbenzo[d]oxazole and 2-arylbenzo[d]thiazole has been achieved through Ru(II)-catalyzed alkenylation with unactivated olefins leading to selective formation of the mono-alkenylated products. This approach has a broad substrate scope with respect to the coupling partners, affords high yields, and works for gram scale synthesis using a readily available Ru-based catalyst. Mechanistic studies reveal a C−H activation pathway for the dehydrogenative coupling leading to the alkenylation. However, the results of the ESI-MS-guided deuterium kinetic isotope effect studies indicate that the C−H activation stage may not be the rate-determining step of the reaction. The use of a radical scavenging agent such as TEMPO did not show any detrimental effect on the reaction outcome, eliminating the possibility of the involvement of a free-radical pathway.     

A Molecular Analogue of the C−H Activation Intermediate of the Silica-Supported Ga(III) Single-Site Propane Dehydrogenation Catalyst: Structure and XANES Signature

Propane dehydrogenation is an important field of research due to an increasing world-wide demand of propene while classical production routes through naphtha cracking are in decline. In that context, silica-supported Ga(III) sites, synthesized from surface organometallic chemistry principles, show high selectivity and stability in the propane dehydrogenation reaction. This performance is in significant contrast to the reported fast deactivation and lower selectivity of most Ga₂O₃ and CrO₃ based materials. The Ga-catalyzed propane dehydrogenation reaction is proposed to proceed through the formation of Ga alkyl intermediates for which it would be desirable to have detailed structural and spectroscopic information. Here, we prepare a consistent series of Ga(III) molecular complexes with varying numbers of alkyl and siloxide ligands; they are characterized by single crystal X-Ray diffraction and X-Ray Absorption Near Edge Structure analysis, which is known to be highly sensitive to the Ga coordination environment. We report in particular the structure and the spectroscopic signatures of [Ga(ⁱPr)(OSi(O^tBu)₃)₂(HOSi(O^tBu)₃)], a molecular mimic of the key proposed reaction intermediates in the Ga-catalyzed PDH reaction.     

The Deuterated “Magic Methyl” Group: A Guide to Site-Selective Trideuteromethyl Incorporation and Labeling by Using CD3 Reagents

In the field of medicinal chemistry, the precise installation of a trideuteromethyl group is gaining ever-increasing attention. Site-selective incorporation of the deuterated “magic methyl” group can provide profound pharmacological benefits and can be considered an important tool for drug optimization and development. This review provides a structured overview, according to trideuteromethylation reagent, of currently established methods for site-selective trideuteromethylation of carbon atoms. In addition to CD₃, the selective introduction of CD₂H and CDH₂ groups is also considered. For all methods, the corresponding mechanism and scope are discussed whenever reported. As such, this review can be a starting point for synthetic chemists to further advance trideuteromethylation methodologies. At the same time, this review aims to be a guide for medicinal chemists, offering them the available C−CD₃ formation strategies for the preparation of new or modified drugs.     

Predicting Regioselectivity in Radical C−H Functionalization of Heterocycles through Machine Learning

Radical C−H bond functionalization provides a versatile approach for elaborating heterocyclic compounds. The synthetic design of this transformation relies heavily on the knowledge of regioselectivity, while a quantified and efficient regioselectivity prediction approach is still elusive. Herein, we report the feasibility of using a machine learning model to predict the transition state barrier from the computed properties of isolated reactants. This enables rapid and reliable regioselectivity prediction for radical C−H bond functionalization of heterocycles. The Random Forest model with physical organic features achieved 94.2 % site accuracy and 89.9 % selectivity accuracy in the out-of-sample test set. The prediction performance was further validated by comparing the machine learning results with additional substituents, heteroarene scaffolds and experimental observations. This work revealed that the combination of mechanism-based computational statistics and machine learning model can serve as a useful strategy for selectivity prediction of organic transformations.     

para-Selective Arylation of Arenes: A Direct Route to Biaryls by Norbornene Relay Palladation

Biaryl compounds are extremely important structural motifs in natural products, biologically active components and pharmaceuticals. Selective synthesis of biaryls by distinguishing the subtle reactivity difference of distal arene C−H bonds are significantly challenging. Herein, we describe para-selective C−H arylation, which is acheived by a unique combination of a meta-directing group and norbornene as a transient mediator. Upon direct meta-C−H palladation, one-bond relay palladation occurs in presence of norbornene and subsequently para-C−H arylation is achieved for sulfonates, phosphonates and phenols bearing 2,6-disubstitution patterns. The protocol is amenable to electron-deficient aryl iodides. Multisubstituted arenes and phenols are obtained by postsynthetic modification of the products. The protocol allows the synthesis of hexa-substituted benzene by sequential selective distal C−H functionalization.     

Enantioselective CpxRhIII-Catalyzed Carboaminations of Acrylates

Enantioselective carboaminations of olefins constitute an attractive strategy for a rapid increase in molecular complexity from readily available starting materials. Reported here is an intermolecular asymmetric carboamination of acrylates using rhodium(III)-catalyzed alkenyl C−H activations of N-enoxysuccinimides to generate the nitrogen and carbon portion for the transfer. A rhodium complex equipped with a tailored bulky trisubstituted chiral Cp^x ligand ensures carboamination chemoselectivity as well high levels of enantioinduction. The transformation operates under mild reaction conditions at ambient temperatures and provides access to a variety of α-amino esters in good yields and excellent enantiomeric ratios of >99.5:0.5.     

N−H Bond Formation at a Diiron Bridging Nitride

Despite their connection to ammonia synthesis, little is known about the ability of iron-bound, bridging nitrides to form N−H bonds. Herein we report a linear diiron bridging nitride complex supported by a redox-active macrocycle. The unique ability of the ligand scaffold to adapt to the geometric preference of the bridging species was found to facilitate the formation of N−H bonds via proton-coupled electron transfer to generate a μ-amide product. The structurally analogous μ-silyl- and μ-borylamide complexes were shown to form from the net insertion of the nitride into the E−H bonds (E=B, Si). Protonation of the parent bridging amide produced ammonia in high yield, and treatment of the nitride with PhSH was found to liberate NH₃ in high yield through a reaction that engages the redox-activity of the ligand during PCET.     

Composition-Tunable Antiperovskite CuxIn1−xNNi3 as Superior Electrocatalysts for the Hydrogen Evolution Reaction

A group of newly reported antiperovskite nitrides Cu_xIn_1−xNNi₃ (0≤x≤1) with tunable composition are employed as electrocatalysts for the hydrogen evolution reaction (HER). Cu_0.4In_0.6NNi₃ shows the highest intrinsic performance among all developed catalysts with an overpotential of merely 42 mV at 10 mA cm_geo⁻². Stability tests at a high current density of 100 mA cm_geo⁻² show its super-stable performance with only 7 mV increase in overpotential after more than 60 hours of measurement, surpassing commercial Pt/C (increase of 170 mV). By partial substitution, the derived antiperovskite nitride achieves a smaller kinetic barrier of water dissociation compared to the unsubstituted InNNi₃ and CuNNi₃, revealed by first-principle calculations. It is found that the partially substituted Cu_xIn_1−xNNi₃ possesses a thermal neutral and desirable Gibbs free energy of hydrogen for HER, ascribed to the tailoring of the energy of d-band center arose by the A-site (A=Cu or In) substitution and a resulting optimization of adsorbate interactions.     

Facile Preparation of WO3−x Dots with Remarkably Low Toxicity and Uncompromised Activity as Co-reactants for Clinical Diagnosis by Electrochemiluminescence

The exceptional nature of WO_3−x dots has inspired widespread interest, but it is still a significant challenge to synthesize high-quality WO_3−x dots without using unstable reactants, expensive equipment, and complex synthetic processes. Herein, the synthesis of ligand-free WO_3−x dots is reported that are highly dispersible and rich in oxygen vacancies by a simple but straightforward exfoliation of bulk WS₂ and a mild follow-up chemical conversion. Surprisingly, the WO_3−x dots emerged as co-reactants for the electrochemiluminescence (ECL) of Ru(bpy)₃²⁺ with a comparable ECL efficiency to the well-known Ru(bpy)₃²⁺/tripropylamine (TPrA) system. Moreover, compared to TPrA, whose toxicity remains a critical issue of concern, the WO_3−x dots were ca. 300-fold less toxic. The potency of WO_3−x dots was further explored in the detection of circulating tumor cells (CTCs) with the most competitive limit of detection so far.