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Category Archives: Applied Organometallic Chemistry
PolyVinyl alcohol and copper nickel co‐doped titania nanocomposite: Designing, characterization, optical properties, and catalytic application in the synthesis of aryl derivatives of benzothiazole and benzimidazole

This paper reports the design, synthesis, properties, and applications of a nanocomposite material composed of polyvinyl alcohol (PVA) and copper nickel co-doped titanium dioxide (Cu-TiO2-Ni). The material was synthesized using a simple precipitation process, and its properties were characterized using various analytical techniques, including powder X-ray diffraction, Fourier transform infrared spectroscopy, thermogravimetry analysis, field emission scanning electron microscopy, and high-resolution tunnelling electron microscopy; BET surface area was investigated. Its application as a catalyst in synthesizing aryl derivatives of benzothiazole and benzimidazoles has been checked.
The paper examines the properties and potential applications of a nanocomposite material composed of polyvinyl alcohol (PVA) and copper nickel co-doped titanium dioxide (Cu-TiO2-Ni). The material was synthesized using a simple precipitation process, and its properties were characterized using various analytical techniques, including powder X-ray diffraction, Fourier transform infrared spectroscopy, thermogravimetry analysis, field emission scanning electron microscopy, and high-resolution tunnelling electron microscopy; Brunauer–Emmett–Teller (BET) surface area was investigated. The results showed that the addition of Cu-TiO2-Ni to PVA improved the material's Ultraviolet–visible spectroscopy (UV) absorption properties. Additionally, the PVA/Cu-TiO2-Ni nanocomposite material exhibited potential for use in a range of applications, including catalysis. Its utility in synthesizing aryl derivatives of benzothiazole and benzimidazoles, which are crucial intermediates in the fine chemical, agrochemical, and pharmaceutical industries and material science, was evaluated. It was found to offer several advantages, including a quick reaction time, simple workup, and good to excellent isolated yields. These characteristics make this protocol both practical and economically intriguing.
Anthracene appended organotin (IV) compounds: Synthesis, structure elucidation and their cytotoxicity against A549 and RBL cancer cell lines

In vitro, cytotoxicity evaluation of two new anthracene Schiff base triorganotin(IV) compounds are reported. Molecular docking studies suggest their interaction with Hsp90 and NF-κB p65 proteins. One of the compounds demonstrates a notable inhibitory effect on the proliferation of A-549 (lung carcinoma) cells, and has a strong affinity for those proteins.
Two new anthracene Schiff base triorganotin (IV) compounds trimethylstannyl(E)-4-((anthracen-9-ylmethylene)amino)benzoate (1) and triphenylstannyl(E)-4-((anthracen-9-ylmethylene)amino)benzoate (2) were synthesized by mixing trimethylstannyl (or triphenylstannyl) 4-aminobenzoate and 9-anthraldehyde in anhydrous toluene under refluxing conditions. Elemental analysis, FT-IR, 1H-NMR, 119Sn NMR and ESI-MS were used to determine the composition of the compounds. X-ray diffraction analyses revealed the structural details of the compounds. The in vitro cytotoxicity assessment of these compunds was screened against human A-549 (lung carcinoma) and rat RBL (leukemia) cancer cell lines. Both compounds displayed a pronounced in vitro cytotoxic effect on the subjected cancer cell lines. Notably, the proliferation of A-549 cells experienced substantial inhibition in the presence of compound 2. The mode of interaction with Hsp90 and NF-κB p65 proteins responsible for cancer propagation was also assessed by molecular docking. Compounds 1 and 2 bind to the Hsp90 protein with binding energies of −307.65 and −373.45 kcal/mol, respectively, while to NF-κB p65 protein the binding energies are of −329.35 and −395.35 kcal/mol, in the same order. Compound 2 exhibited a significantly high binding affinity to NF-κB p65 and Hsp90 proteins validating our experimental findings from the in vitro experiments.
Recent progress of nanocatalyst in the synthesis of heterocyclic compounds by barbituric acids

Heterocycles and barbituric acid analogs are particularly used in developing and designing new drugs because of their versatile binding properties for different biotargets. They are present in many natural compounds, vitamins, drugs, and biologically active molecules such as anticancer, antibiotic, antidiabetic, anti-inflammatory, antidepressant, anti-HIV, antimicrobial, and insecticidal agents. Using co-friendly techniques under nanocatalyst conditions drives the synthesis of these bioactive compounds toward green chemistry. This review will investigate the nanocatalysts, including magnetic nanocatalysts, nano metal-based catalysts, organo-nanocatalysts, and metal–organic frameworks (MOFs) nanocatalysts employed in the synthesis and design of heterocyclic compounds by barbituric acids from 2017 to 2022.
Heterocycles and barbituric acid analogs are particularly used in developing and designing new drugs because of their versatile binding properties for different biotargets. They are present in many natural compounds, vitamins, drugs, and biologically active molecules such as anticancer, antibiotic, antidiabetic, anti-inflammatory, antidepressant, anti-HIV, antimicrobial, and insecticidal agents. Using co-friendly techniques under nanocatalyst conditions drives the synthesis of these bioactive compounds toward green chemistry. This review will investigate the nanocatalysts, including magnetic nanocatalysts, nano metal-based catalysts, organo-nanocatalysts, and metal–organic frameworks (MOFs) nanocatalysts employed in the synthesis and design of heterocyclic compounds by barbituric acids from 2017 to 2022.
Tumor‐pH‐value responsive non‐peripheral substituted phthalocyanines: Synthesis, investigation of photophysical and photochemical properties

Cancer is one of the diseases with the highest mortality rate worldwide. Although PDT has recently produced encouraging outcomes, there are still many areas that need to be improved. The first of these is the negative consequences faced by patients treated with the PDT method when exposed to sunlight. For this reason, a new PDT method has been developed in recent years, and it is aimed at using photosensitizer molecules that can be active in acidic conditions. Since the pH values of tumor tissues are more acidic than normal tissues, preparing molecules that act effectively in acidic conditions will allow for more effective results in treating cancer with PDT. In this context, within the scope of this study, 3-(4-propionylphenoxy)phthalonitrile (1) and its non-peripheral tetra-substituted phthalocyanine derivatives [(2), (3), and (4)] were prepared. With these phthalocyanine derivatives, the novel compounds (5), (6), and (7) were synthesized for the first time. The aggregation tendencies of newly synthesized phthalocyanines (5–7) were investigated in solvent media. The effects of pH changes upon UV–Vis and fluorescence spectra were performed. The electronic and emission spectra of synthesized phthalocyanine derivatives are highly sensitive to pH changes. Formation constant (LogK) values of mono- and di-protonated phthalocyanine forms were calculated by the Henderson–Hasselback equation. The mono- and di-protonated species' equilibrium constants (logK1 and logK2) were calculated as ~5.0. This value may be promising for pH-sensitizing photosensitizers. Also, the photophysical and photochemical properties of synthesized metallophthalocyanine derivatives (2) and (5) were studied at different pH values. The singlet oxygen quantum yield of (2) and (5) was calculated to be 0.78 and 0.81 in DMSO, respectively. When pH = 6.4, that is, tumor-pH-values, this value for (5) has increased to 0.92. The newly synthesized phthalocyanines are suitable photosensitizers for PDT applications, especially with high singlet oxygen quantum yield at pH 6.4.
Green synthesis and theoretical study of new 1,3,4‐oxadiazoles: Application of Cu/Fe3O4@MWCNT magnetic nanocomposites

Cu/Fe3O4@MWCNT MNCs as an effective catalyst was synthesized by using water extract of Petasits hybridus leaves and promoted producing of novel derivatives of 1,3,4-oxadiazols in high yields. These new compounds were synthesized by using multicomponent reaction of ninhydrins, diamines or hydroxyamines, ester of acetylene with electron deficient, α-haloketones, hydrazoyl chloride and synthesized nanocatalyst in aqueous media. It should be mentioned that the high performance of nanocatalyat was synthesized by using water extract of Petasits hybridus leaves, which was utilized in these reactions for many times to confirm the reusability of nanocatalyst.
Cu/Fe3O4@MWCNT magnetic nanocomposites (MNCs) as an effective catalyst was promoted producing of novel derivatives of 1,3,4-oxadiazols in high yields. These new compounds were synthesized by using multicomponent reaction of ninhydrins, diamines or hydroxyamines, ester of acetylene with electron deficient, α-haloketones, hydrazoyl chloride, and synthesized nanocatalyst in aqueous media. It should be mentioned that the high performance of nanocatalyat was synthesized by using water extract of Petasits hybridus leaves, which was utilized in these reactions for many times to confirm the reusability of nanocatalyst. The antioxidant property of new synthesized 1,3,4-oxadiazols is owing to having NH group which was evaluated by two procedures named diphenyl-picrylhydrazine (DPPH) radical trapping and Ferric ions (Fe3+) reducing potential (FRAP) experiment. Also, the antimicrobial activity of new generated 1,3,4-oxadiazols was evaluated by disk distribution process utilizing two kinds of Gram-negative bacteria and Gram-positive bacteria, proving bacterial growth was stopped by using of these compounds. This employed procedure for preparation of 1,3,4-oxadiazols derivatives conveys benefits including reaction with low time, products with high yields, and possibility of separating catalyst and products using an easy procedure.
Photoinduced electron transfer reaction for synthesis of tetrahydroquinoline derivatives with conjugated structure using chlorophyll b‐modified magnetic titanium dioxide photocatalyst

In this study, the chlorophyll b-modified magnetic titanium dioxide photocatalyst was designed to synthesize conjugated derivatives of tetrahydroquinoline through a photoinduced electron transfer (PET) reaction. The prepared photocatalyst was highly active under visible-light irradiation toward the cyclization of (E)-3-[4-(dimethylamino)phenyl)]-1-arylprop-2-en-1-one with 1-aryl-1H-pyrrole-2,5-dione to achieve new tetrahydroquinoline derivatives with conjugated structure in high yields at ambient temperature, in air. The magnetic property enabled easy recovery of the photocatalyst and improved its reusability up to three runs.
Photocatalytic conversion of organic compounds has recently emerged as a cost-effective, safe, and easy-to-operate procedure to synthesize value-added materials. In this study, the magnetic titanium dioxide-based (Fe3O4/SiO2/TiO2) photocatalyst was designed to synthesize conjugated derivatives of tetrahydroquinoline through a photoinduced electron transfer (PET) reaction. Chlorophyll b was immobilized on the surface of magnetic titanium dioxide, as a natural visible-light-sensitive compound using 3-aminopropyltriethoxysilane (APTES) as a coupling agent containing terminal amine (Fe3O4/SiO2/TiO2-NH2-Chb) to improve light harvesting ability. Fourier transform infrared (FT-IR), powder X-ray diffraction (PXRD), thermogravimetric analysis (TGA), energy-dispersive X-ray spectrometer (EDS), and vibrating sample magnetometer (VSM) results confirmed the successful synthesis of Fe3O4/SiO2/TiO2-NH2-Chb. Scanning electron microscope (SEM) and transmission electron microscope (TEM) images displayed the preserved spherical morphology of Fe3O4/SiO2/TiO2-NH2-Chb. Chlorophyll b-modified magnetic titanium dioxide was highly active under visible-light irradiation toward the cyclization of (E)-3-[4-(dimethylamino)phenyl)]-1-arylprop-2-en-1-one with 1-aryl-1H-pyrrole-2,5-dione to achieve new tetrahydroquinoline derivatives with conjugated structure in high yields at ambient temperature, in air. The incorporation of chlorophyll b in the photocatalyst plays an important role in the photocatalytic mechanism, facilitating photoinduced electron transfer to the conduction band of TiO2. Moreover, the magnetic property enabled easy recovery of the photocatalyst and improved its reusability up to three runs. The characteristics of tetrahydroquinoline derivatives were studied by FT-IR, CHN, 1H NMR, and 13C NMR analyses.
Chain‐walking polymerization of ethylene and 1‐octene with ortho‐phenyl‐based α‐diimine Ni (II) catalysts

The ortho-phenyl-substituted Ni catalysis system based on α-diimine with variable electronic nature are highly active toward ethylene polymerization to synthesize high molecular weight polyethylene, and conducted the chain-walking polymerization of 1-octene to produce highly branched polyolefins.
A class of ortho-phenyl-substituted Ni (II) α-diimine complexes with variable electronic nature in the 4-phenyl position, {[(4-Me-2-(4-R-C6H4)C6H3N=C)2Naphth]NiBr2, R = OMe (C1); R = Me (C2); R = H (C3)}, was prepared and characterized. These nickel dibromide complexes were confirmed by X-ray crystallography analysis and crystallized as a centrosymmetric bromine-bridged dimer in a distorted tetrahedral geometry at the two Ni (II) centers connected by a four-membered ring. Because of the conjugation effect and steric hindrance effect of ortho-phenyl substituent, these Ni-Et2AlCl systems via controlled chain-walking ethylene polymerization performed with high catalytic activities of up to 3.10 × 106 g PE (mol Ni h)−1 to yield high molecular weight branched PEs with narrow M w/M n values (PDI ≤ 2.39). This Ni (II) system also conducted the chain-walking polymerization of 1-octene, resulting in highly branched polyolefins (up to 107 branches/1000C).
Novel core–shell magnetic nanoparticles@Zeolitic imidazolate with glycerol‐nickel for the synthesis of dihydropyrimidinones

A novel Fe3O4-ZIF-8@Glycerol-Ni nanocatalyst was synthesized. Highly efficient catalytic activity was acquired for synthesizing dihydropyrimidinones with ethanol as suitable solvent in the reaction.
The present study reported a novel and eco-friendly synthesis of Fe3O4@ZIF-8@Glycerol-Ni nanocatalyst via a multistep process. The as-prepared catalyst was used due to its high efficiency, low cost, and biocompatibility for the fabrication of dihydropyrimidinones by Biginelli multicomponent reactions of aryl aldehyde, ethyl acetoacetate, and urea under ambient status. X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), Brunauer-Emmet-Teller (BET), vibrating sample magnetometry (VSM), scanning electron microscopy and energy dispersive X-ray (SEM-EDS), inductively coupled plasma (ICP), elemental mapping analysis (EMA), thermogravimetric analysis (TGA), Raman, and transmission electron microscopy (TEM) techniques were successfully utilized to evaluate the nanocatalyst. The advent of the peaks confirmed the presence of nickel on the catalyst's surface due to the oxygen and nickel, and the nanoparticle size is 10–15 nm. Eventually, nano-heterogeneous catalyst exhibits high performance as well as good selectivity in the synthesis of dihydropyrimidinones. Also, it can be recycled up to multiple fresh runs with no significant loss of catalytic efficiency.
Gemini surfactant‐stabilized Pd nanoparticles: Synthesis, characterization, and catalytic application in the reduction and reductive acetylation in the water solvent

The organogels have been prepared using long-chain gemini surfactants. Their rheological properties such as amplitude sweeping and viscosity shear profile have been studied. Further reductive acetylation was carried out in an aqueous medium using Pd NPs stabilized by organogels.
A series of Gemini surfactants (GSs) were prepared by reacting alkyl bromides with N,N,N′,N′-tetramethyl ethylenediamine. Various alkyl bromides used in for the preparation of GSs are 1,3-dibromo ethane, 1,3-dibromoethane, 1-Bromohexane, 1-Bromooctane, 1-Bromooctadecane and 1-Bromooctadodecane. Different solvents and temperatures were investigated for the formation of gels of prepared GSs. Among all, 1-Bromooctane, 1-Bromooctadecane-derived GSs formed organogels. Thus, synthesized long-chain organogels have been used to stabilize Pd NPs. The Pd NPs formation initially confirmed through Ultraviolet-visible, Scanning Electron Microscopy, and Atomic Force Micrograph studies. Later Fourier Tansform Infra Red, Thermo Gravimetric Analysis, and Zeta potential studies were also carried out to understand their properties extensively. The Pd NPs stabilized by GSs have been identified as a potential catalyst in the reductive N-acetylation of nitroaromatics at room temperature. The N-acetylated products were obtained in good yields in an aqueous medium. In addition, the potentiality of our catalyst has been also evaluated in the reduction of nitroaromatics in an aqueous medium, which is a green protocol. Further, the semi-empirical geometry optimizations of active GS gel confirmed the dihedral angle of 59° in between the two octyl moieties calculated from computational studies. The rheological properties such as amplitude sweeping, viscosity shear profile of the gel have also been studied.