Synergistic Nanoscale Mn3O4-CoO-Co Heterojunctions for Boosting the Selectivity in Hydrogenation of Nitrostyrenes and Nitroarenes.

Metal-metal oxide interface catalysts are in high demand for advanced catalytic applications due to their multi-component active sites, which facilitate synergistic cooperation where a single component alone cannot effectively promote the desired reaction. Demonstrated herein graphene oxide-supported nanoscale Mn3O4-CoO-Co as highly efficient catalysts for hydrogenation of nitro styrenes/nitro arenes to amino styrenes/arenes under mild reaction conditions (0.5 MPa and 100 °C in 1:1 THF/water). Charge relocalization at the Co-CoO-Mn3O4 heterojunction interfaces, primarily driven by Mn3O4, significantly improves reaction selectivity. Replacing Mn3O4 with MnO or using other supported bimetallic CoMnOx catalysts decreases selectivity, leading to the formation of a mixture of products. The catalyst demonstrated remarkable selectivity in converting nitro groups to amines, even in the presence of highly reactive functional groups such as C=C, O-C=O, C=O, C≡N, chalcones, and halides. It also exhibited high yields, multiple reusability, and a broad substrate scope. This study demonstrates how Mn3O4, in synergy with CoO-Co, fine-tunes selectivity, paving the way for the development of advanced metal-metal oxide interface catalysts to enhance both selectivity and efficiency in organic transformations.

Enhancing Precatalyst Performance and Robustness through Aromaticity: Insights from Iridaheteroaromatics.

Despite the inherent stability-enhancing benefits of dπ-pπ conjugation-induced aromaticity, metallaaromatic catalysts remain underutilized in this context, despite their reactivity with organic functionalities in stoichiometric reactions. We present a strategy for synthesizing a diverse range of iridaheteroaromatics, (L^L)IrIII(Cp*)I, including iridapyridylidene-indole, iridapyridene-indole, and iridaimidazole, via in situ deprotonation/metalation reactions utilizing [Cp*IrCl2]2 and the respective ligands. These catalysts exhibit enhanced σ-donor and π-acceptor properties, intrinsic σ-π continuum attributes, and versatile binding sites, contributing to stability through enhanced dπ-pπ conjugation-induced aromaticity. Spectroscopic data, X-ray crystallographic data, and density functional theory calculations confirm their aromaticity. These iridaheteroaromatics exhibit formidable catalytic ability across a spectrum of transformations under industrially viable conditions, notably excelling in highly selective cross alkylation and ß-alkylation of alcohols and an eco-friendly avenue for quinolone synthesis, achieving remarkably high turnover frequencies (TOFs). Additionally, this method extends to the self-condensation of bioalcohols like ethanol, n-butanol, and n-hexanol in water, replicating conditions frequently encountered in primary fermentation solutions. These iridaheteroaromatics exhibit strong catalytic activity with fast reaction rates, high TOFs, broad substrate compatibility, and remarkable selectivity, displaying their potential as robust catalysts in large-scale applications and emphasizing their practical significance beyond their structural and theoretical importance.

Co-Ti Bimetallic Complex-Induced Phase Modulation of Co@Black TiO2 for Catalytic Hydrogenation of Cinnamaldehyde.

Transition-metal-doped black titania, primarily in the anatase phase, shows promise for redox reactions, water splitting, hydrogen generation, and organic pollutant removal, but exploring other titania phases for broader catalytic applications is underexplored. This study introduces a synthetic approach using a Co-Ti bimetallic complex bridged by a 1,10-phenanthroline-5,6-dione ligand as a precursor for the synthesis of cobalt-doped black titania [Co@L2N@b-TiO2]. The synthesis involves precise control of pyrolysis conditions, yielding a distinct structure dominated by the rutile phase over anatase, with active cobalt encapsulated within a nitrogen-doped graphitic layer, primarily as Co0 rather than CoII and CoIII. The synthesized material is employed for the selective hydrogenation of cinnamaldehyde (CAL) to cinnamyl alcohol (COL) under industrially viable conditions. The efficiency and selectivity of Co@L2N@b-TiO2 was compared with other catalysts, including cobalt-doped rutile TiO2 (Co@r-TiO2), anatase TiO2 (Co@a-TiO2), and black titania (Co@b-TiO2) as well as materials pyrolyzed under different atmospheres and temperatures, materials with phenanthroline ligands, and materials lacking any ligands. The superior performance of Co@L2N@b-TiO2 is attributed to its high surface area, stable Co0 within the nitrogen-doped graphitic layer, and composition of rutile and anatase phases of TiO2 and Ti2O3 (referred to as RAT), along with the synergistic interaction between RAT and Co0. These factors significantly influence the efficiency and selectivity of COL over hydrocinnamaldehyde (HCAL) and hydrocinnamyl alcohol (HCOL), indicating potential for broader applications beyond catalysis, particularly in designing of black titania-based materials.

Intermetallic Pd-Sn Nanoparticles on Supports with High Metal Loading Facilitated by the Metal-Metal Bond for High-Performance Cooperative Catalysis.

Atomically monodispersed intermetallic catalysts comprising highly accessible active sites are ideal heterogeneous catalytic materials. Designing such types of nanocatalysts on carbonaceous supports with high loading, however, remains a formidable challenge. Demonstrated herein is an effective synthetic strategy to produce highly dispersed intermetallic Pd-Sn nanoparticles on various supports with high catalyst loading (upto 24 wt % Pd and 18 wt % Sn) using a discrete bimetallic Pd-Sn complex, which in turn is highly superior as compared to conventionally used methods using individual metal salts. Synergistic cooperative interaction between sub-5 nm Pd-rich particles, supports, and large intermetallic Pd-Sn particles allowed their electronic cross-talk, displaying a much higher reaction efficiency with an entirely different selectivity toward a product, which is highly unlikely in the case of comparable individual components or sequentially impregnated bimetallic materials involving in a catalytic/photocatalytic dehydrogenation, hydrogenation, tandem (de)hydrogenation, and amidation reaction. The designed synthetic strategy has the potential to contribute to the development of atomically monodispersed intermetallic high-loading functional materials for advanced electro- and photocatalytic applications.

Tetrametallic Copper Complex to Nanoscale Copper: Selective and Switchable Dehydrogenation-Hydrogenation under Light.

A discrete, photoactive, ultrafine copper nanocluster of fewer than hundreds of atoms with stimuli-responsive switchable redox-active states is highly desired to control two different antagonistic reactions. Herein, a mixed-valent tetrametallic copper complex (C-1) of N-O-N Schiff base ligand is disclosed, in which the five different Cu-Cu interactions were used to generate photoactive nanoscale copper [LCu0 n , S-1] through the reduction of coordinated imine to the amine of C-1. The presence of a ligand provides stability and helps to homogenize the material (S-1) in the organic solvent. The cluster showed stimuli (O2 /light)-responsive switching between its reduced (S-1) and oxidized [LCu0 n-m CuOm , S-2] states that allows it to serve as a highly and poorly active (bistate, relative rate >5-12 fold) catalyst for the dehydrogenation of alcohols to aldehydes and hydrogenation of nitroaromatics to amino aromatics under the light.

Ruthenium(II)-Catalyzed Hydrogenation and Tandem (De)Hydrogenation via Metal-Ligand Cooperation: Base- and Solvent-Assisted Switchable Selectivity.

A versatile, selective, solvent (methanol vs ethanol)- and base (potassium vs lithium carbonate)-assisted switchable synthesis of saturated ketone and α-methyl saturated ketone from α,ß-unsaturated ketone is developed. Mechanistic aspects, evaluated from spectroscopic studies, in situ monitoring of the reaction progress, control studies, and labeling studies, further indicate the involvement of a tandem dehydrogenation-condensation-hydrogenation sequence in the reaction, in which the interconvertible coordination mode (imino N → Ru and amido N-Ru) of coordinated imidazole with Ru(II)-para-cymene is crucial, without which the efficiency and selectivity of the catalyst are completely lost. The catalyst demonstrates good efficiency, selectivity, and functional group tolerance and displays a broad scope (69 examples) for monomethylation and hydrogenation of unsaturated chalcones, double methylation of ketones, and N-methylation of amines.

Inhibition of copper-mediated aggregation of human γD-crystallin by Schiff bases.

Protein aggregation, due to the imbalance in the concentration of Cu2+ and Zn2+ ions is found to be allied with various physiological disorders. Copper is known to promote the oxidative damage of ß/γ-crystallins in aged eye lens and causes their aggregation leading to cataract. Therefore, synthesis of a small-molecule 'chelator' for Cu2+ with complementary antioxidant effect will find potential applications against aggregation of ß/γ-crystallins. In this paper, we have reported the synthesis of different Schiff bases and studied their Cu2+ complexation ability (using UV-Vis, FT-IR and ESI-MS) and antioxidant activity. Further based on their copper complexation efficiency, Schiff bases were used to inhibit Cu2+-mediated aggregation of recombinant human γD-crystallin (HGD) and ß/γ-crystallins (isolated from cataractous human eye lens). Among these synthesized molecules, compound 8 at a concentration of 100 µM had shown ~95% inhibition of copper (100 µM)-induced aggregation. Compound 8 also showed a positive cooperative effect at a concentration of 5-15 µM on the inhibitory activity of human αA-crystallin (HAA) during Cu2+-induced aggregation of HGD. It eventually inhibited the aggregation process by additional ~20%. However, ~50% inhibition of copper-mediated aggregation of ß/γ-crystallins (isolated from cataractous human eye lens) was recorded by compound 8 (100 µM). Although the reductive aminated products of the imines showed better antioxidant activity due to their lower copper complexing ability, they were found to be non-effective against Cu2+-mediated aggregation of HGD.

PdII/AgI-Catalyzed Room-Temperature Reaction of γ-Hydroxy Lactams: Mechanism, Scope, and Antistaphylococcal Activity.

The present work reports a PdII/AgI-promoted amidoalkylation reaction involving various γ-hydroxy lactams and C/O/S nucleophiles at room temperature. The dual mode of activation of both the electrophile and nucleophile by in situ generated catalytically active cationic PdII species facilitates the reaction at room temperature. Among the synthesized isoindoline derivatives, three compounds are found to be active against vancomycin and methicillin-resistant S. aureus strain with appreciable MIC values.

Novel boronic acid derivatives of bis(indolyl) methane as anti-MRSA agents.

Towards the search for a new generation of antibiotics to control methicillin-resistant Staphylococcus aureus (MRSA), the design and synthesis of various bis indolyl methane (BIM) derivatives based on their different electron donor and acceptor properties of the substituents have been made, in which boronic acid derivatives of BIM are found to be active against MRSA. The observed evidence with the lead compound reveals their strong anti-MRSA activity, which paves the way of design and further development of a new generation antibiotics.

Triggering the approach of an arene or heteroarene towards an aldehyde via Lewis acid-aldehyde communication.

The present work reports a combined experimental/computational study of the Lewis acid promoted hydroxyalkylation reaction involving aldehyde and arene/heteroarene and reveals a mechanism in which the rate determining aldehyde to alcohol formation via a four-member cyclic transition state (TS) involves a transfer of hydrogen from arene/heteroarene C-H to aldehyde oxygen with the breaking of the C-H bond and formation of C-C and O-H bonds. The effect of different Sn(iv) derivatives on the hydroxyalkylation reaction from different in situ NMR and computational studies reveals that although the exergonic formation of the intermediate and its gained electrophilicity at the carbonyl carbon drive the reaction in SnCl4 compared to other Sn(iv) derivatives, the overall reaction is low yielding because of its stable intermediate. With respect to different aldehydes, LA promoted hydroxylation was found to be more feasible for an electron withdrawing aldehyde compared to electron rich aldehyde because of lower stability, enhanced electrophilicity gained at the aldehyde center, and a lower activation barrier between its intermediate and TS in the former as compared to the latter. The relative stability of the LA-aldehyde adduct decreases in the order SnCl4 > AlCl3 > InCl3 > BF3 > ZnCl2 > TiCl4 > SiCl4, while the activation barrier (ΔG(#)) between intermediate and transition states increases in the order AlCl3 < SnCl4 < InCl3 < BF3 < TiCl4 < ZnCl2 < SiCl4. On the other hand, the activation barriers in the case of different arenes/heteroarenes are in the order of indole < furan < anisole < thiophene < toluene < benzene < chlorobenzene < cyanobenzene, which suggests a facile reaction in the case of indole and the most difficult reaction in the case of cyanobenzene. The ease of formation of the corresponding diaryl methyl carbocation from the alcohol-LA intermediate is responsible for the determination of the undesired product and is found to be more viable in the case of strong LAs like AlCl3, InCl3 and SnCl4 because they have negative free energy of formation (ΔG) for alcohol to the corresponding diaryl methyl carbocation.

Electrophilicity and nucleophilicity of commonly used aldehydes.

The present approach for determining the electrophilicity (E) and nucleophilicity (N) of aldehydes includes a kinetic study of KMNO4 oxidation and NaBH4 reduction of aldehydes. A transition state analysis of the KMNO4 promoted aldehyde oxidation reaction has been performed, which shows a very good correlation with experimental results. The validity of the experimental method has been tested using the experimental activation parameters of the two reactions. The utility of the present approach is further demonstrated by the theoretical versus experimental relationship, which provides easy access to E and N values for various aldehydes and offers an at-a-glance assessment of the chemical reactivity of aldehydes in various reactions.

Heterobimetallic Pd-Sn catalysis: Michael addition reaction with C-, N-, O-, and S-nucleophiles and in situ diagnostics.

An efficient Michael addition reaction of differently substituted enones with carbon, sulfur, oxygen, and nitrogen nucleophiles has been achieved by a new heterobimetallic "Pd-Sn" catalyst system. The nature of the catalytically relevant species and their interactions with the enone moiety has been examined by spectroscopy. The effect of ligand and the coordination mode of enone with "Pd-Sn" heterobimetallic system have been investigated by kinetics and DFT studies. A straightforward application of this methodology is shown in the synthesis of 1,4-oxathiepane core.

Kaajal fights against eye pathogens and is safe for eye make-up: a reinvestigation of an ancient practice.

The present report includes a scientific view of the traditional use of 'Kaajal' from the leaf of Euphorbia neriifolia, an Indian spurge tree locally called the 'Monosha' plant. A thorough analysis of the material demonstrates that it contains carbon nanoparticles having two uniform sizes of 2-3 nm and 35-45 nm. Further study revealed that Kaajal has antimicrobial properties against eye pathogens and is biocompatible for cosmetic use.

Industrial Grade Resin as Reusable Catalyst for Amidoalkylation of γ-Hydroxy Lactams.

Herein, we disclose a selective, versatile, accessible, cost-effective and highly efficient cation-exchange industrial grade INDION 130 resin as a reusable catalyst for the synthesis of 3-substituted isoindolinones from various γ-hydroxy lactams and a variety of C, N, O, and S nucleophiles involving N-acyliminium ion intermediates under mild reaction conditions. Mechanistic studies suggested the generation of a different kind of kinetically and thermodynamically controlled intermediates/eliminated products, which further converted to their corresponding products depending upon the nucleophile, reaction parameter and nitrogen substitution (benzyl vs. aryl) of the substrate (succinamidals vs. phthalimidals). The easy synthesis, efficient reactivity and selectivity, broad substrate scope with verities of C, N, O, and S nucleophiles, and efficient recycling make the catalyst and the protocol economical and sustainable.

Nanoscale Ni-NiO-ZnO Heterojunctions for Switchable Dehydrogenation and Hydrogenation through Modulation of Active Sites.

Catalysts consisting of metal-metal hydroxide/oxide interfaces are highly in demand for advanced catalytic applications as their multicomponent active sites will enable different reactions to occur in close proximity through synergistic cooperation when a single component fails to promote it. To address this, herein we disclosed a simple, scalable, and affordable method for synthesizing catalysts consisting of nanoscale nickel-nickel oxide-zinc oxide (Ni-NiO-ZnO) heterojunctions by a combination of complexation and pyrolytic reduction. The modulation of active sites of catalysts was achieved by varying the reaction conditions of pyrolysis, controlling the growth, and inhibiting the interlayer interaction and Ostwald ripening through the efficient use of coordinated acetate and amide moieties of Zn-Ni materials (ZN-O), produced by the reaction between hydrazine hydrate and Zn-Ni-acetate complexes. We found that the coordinated organic moieties are crucial for forming heterojunctions and their superior catalytic activity. We analyzed two antagonistic reactions to evaluate the performance of the catalysts and found that while the heterostructure of Ni-NiO-ZnO and their cooperative synergy were crucial for managing the effectiveness and selectivity of the catalyst for dehydrogenation of aryl alkanes/alkenes, they failed to enhance the hydrogenation of nitro arenes. The hydrogenation reaction was influenced by the shape, surface properties, and interaction of the hydroxide and oxide of both zinc and nickel, particularly accessible Ni(0). The catalysts showed functional group tolerance, multiple reusabilities, broad substrate applicability, and good activity for both reactions.

A newly developed highly selective ratiometric fluoride ion sensor: spectroscopic, NMR and density functional studies.

A new easy-to-synthesize chemosensor, 3,3'-bis(indolyl)-4-chlorophenylmethane (hereafter S), was designed, synthesized and employed as a selective optical chemosensor for fluoride ions.(1)H NMR and density functional studies on the system have been carried out to determine the nature of the interaction between S and X(-) (X = inorganic anions) responsible for the significant fluoride-induced changes in the absorption properties of S. The experimental results reveal that abstraction of an acidic proton of S by the fluoride ion, leading to the formation of anionic species, is responsible for the spectral changes. These changes allow signaling for the fluoride ion to detect and estimate the concentration of fluoride ion present even at the submicromolar level, accurate up to 2 µM. Calculations of the transition energies of S, S(-), and S···F(-) (hydrogen bonded complex) show that only S(-) is responsible for the long-wavelength absorption band in the presence of F(-).

First example of a heterobimetallic 'Pd-Sn' catalyst for direct activation of alcohol: efficient allylation, benzylation and propargylation of arenes, heteroarenes, active methylenes and allyl-Si nucleophiles.

Arenes, heteroarenes, 1,3-dicarbonyls and organosilicon nucleophiles undergo highly efficient alkylation with allylic, propargylic and benzylic alcohols in the presence of a new 'Pd-Sn' bimetallic catalyst in nitromethane; water being the sole byproduct. The plausible mechanism of alkylation and the intermediacy of ether has been enumerated.

Ag(I)-catalyzed regioselective ring-opening of N-tosylaziridine and N-tosylazetidine with S-, O-, and N-nucleophiles and tethered dinucleophiles.

[Ag(COD)(2)]PF(6) catalyzes the ring-opening of N-tosylaziridines and -azetidines with alcohols, amines, thiols, and related tethered 1,2-ethane dinucleophiles. Initial rate studies and DFT-based evaluation of stepwise energetics suggest an inverse relationship between the nucleophilic reactivity of a heteroatom donor and its binding affinity to cationic Ag(I).

Nucleophilicity and site selectivity of commonly used arenes and heteroarenes.

By using the inverse concept of electrophilicity and nucleophilicity and with four different available equations from literature for electrophilicity and electrodonating power, the nucleophilicity values of 69 commonly used arenes and heteroarenes have been calculated at the B3LYP/6-311+G(d,p) level of theory. The linearity between the nucleophilicity and Hammett sigma and sigma(p) values has been chosen as a test to judge the goodness of the methods used. Finally four different arene and heteroarene series (substituted indoles, phenols, pyrroles, and anisoles) have been subjected to local nucleophilicity analysis in order to predict the site selectivity in electrophilic aromatic substitution reactions (EAS). In each case we have obtained excellent correlation with the experimental result.

A Remote 'Imidazole'-Based Ruthenium(II) Para-Cymene Pre-catalyst for the Selective Oxidation Reaction of Alkyl Arenes and Alcohols.

Herein we disclosed the use of a remote 'imidazole'-based precatalyst [(para-cymene)RuII (L)Cl]+ , C-1 where L=2-(4-substituted-phenyl)-1H-imidazo[4,5-f][1,10] phenanthroline) for the selective oxidation of a variety of alkyl arenes/heteroarenes and alcohols to their corresponding aldehydes or ketones in presence of tert-butyl hydroperoxide (TBHP). The remote 'imidazole' moiety present in the complex facilitates the activation of oxidant and subsequent generation of active species via the release of para-cymene from C-1, which in-turn was less effective without the 'imidazole' moiety. The mechanistic features of C-1 promoted oxidation of alkyl arenes were also assessed from spectroscopic, kinetic, and few control experiments. The substrate scope for C-1 promoted oxidation reaction was assessed based on the selective oxidation of 27-different alkyl arenes/heteroarenes and 25 different alcohols to their corresponding aldehydes/ketones in moderate to good yields.