Applied Organometallic Chemistry最新文献

N-Arylated heterocyclic molecules are extensively found as key components in numerous pharmaceutical and agrochemical compounds. Herein, inexpensive 1,10-phenanthroline-assisted copper-catalyzed sustainable greener methodology has been developed for N-arylation of indoles and pyrrole under commercial base and additive-free conditions. Waste biomass–derived water extract of banana peel ash (WEB) has been used as safe reaction medium and base instead of hazardous solvents, and hence, the current green protocol has achieved an environmentally benign profile. Reaction of pyrrole with aryl iodides and electronically diverse indoles with aryl iodides/aryl bromides in the presence of CuI as catalyst, 1,10-phenanthroline as ligand, and WEB as a base and solvent at 100°C has furnished N-arylated product within 12 h. Reaction of indoles with aryl iodides furnished up to 93% yields while aryl bromides resulted in up to 54% yield of the desired product. The utilization of waste biomass derivative for organic transformation reaction is the key step of this protocol, which is in consistence with the goals of green chemistry.

In this research, as a new heterogenous nanocomposite, P-doped g-C₃N₄/Cu₂O was successfully synthesized by simultaneous reduction of copper salts and the resultant precipitation. The phosphor was doped onto the graphitic carbon nitrite by the calcination method. The various spectroscopic and imaging methods (XPS, X-ray diffraction [XRD], FTIR, Pl, BET, DRS, Map Scanning, EDS (EDAX), TEM, FESEM, and EIS) were devised to characterize the structural properties, morphology, and optical and photocatalytic activities of the synthesized nanocomposite. The synthesized nanocomposite was then used as photocatalysts in the reduction of nitroaromatic compounds to the corresponding amino aromatic species, with the results being highly promising. Indeed, the conversion of nitrobenzene to aniline was 100% accomplished within 30 min. In these reactions, hydrazine compounds were used as hydrogen suppliers. The proposed photocatalyst exhibits great recyclability and reusability so that no significant change in the catalytic activity of the nanocomposite and the resultant conversion efficiency was observed after six rounds of reuse.

New thiocarbohydrazone ligand (N′-((E)-3,3-diphenyl-2,3-dihydro-1H-inden-1-ylidene)-2-((Z)-2-oxoindolin-3-ylidene)hydrazine-1-carbothiohydrazide; H₂L) and its Co (II), Ni (II), Fe (III), Cu (II), Cd (II), Zn (II), and Mn (II) complexes were prepared in good yields ranging from 60% to 90% and characterized by spectroscopic and analytical tools. Uv–vis, magnetic measurements, molar conductivity, ¹H-NMR spectra, elemental analyses, and FT-IR were performed. The structural formula for the examined ligand was improved using the Gaussian09 tool. The morphology of the thiocarbohydrazone ligand and metal complexes was demonstrated using a scanning electron microscope. The prepared thiocarbohydrazone ligand and its complexes were evaluated for their antimicrobial properties against Streptococcus mutans and Staphylococcus aureus as G-positive bacteria; Escherichia coli, Klebsiella pneumoniae, and Pseudomonas aeruginosa as G-negative bacteria; and some species of fungi as Aspergillus niger and Candida albicans. It was found that thiocarbohydrazone ligand was less biologically active than the targeted complexes as indicated from the obtained inhibition zone diameters. The interaction between the ligand and the amino acids of the proteins of G-positive bacteria (Staphylococcus typhus-3ty7), G-negative bacteria (E. coli-3t88), and fungi (C. albicans-5k04) as receptors was investigated using molecular docking study to correlate the experimental and theoretical observations.

In this research, an effective procedure for the one-pot construction of new quinazoline analogs using chloroacetic acid–immobolized nanocobaltferrite (nano-CoFe₂O₄@SiO₂@CPTES-[(Ph₂PCH₂)₂-CH₂CO₂H]²⁺2Cl⁻) as an efficient novel magnetic nanocatalyst under ultrasound irradiation at 80°C was presented. Chloroacetic acid–immobilized nanocobferrite was characterized by FT-IR, XRD, FE-SEM, TEM, EDX, TGA, VSM, and ICP-mass analyses. Furthermore, the nanocatalyst could be comfortably isolated via magnetic attraction and recycled at least five times without remarkable loss of its catalytic activity. Additionally, in this protocol, quinazoline analogs were screened for their antibacterial activity against Pseudomonas aeruginosa and Staphylococcus aureus. The results showed that quinazolines 4a, 4b, 4c, 4d, and 4g had good antibacterial activity toward Pseudomonas aeruginosa and Staphylococcus aureus.

Non-metallocene catalysts have shown great potential for modulating the polymer microstructure by changing the ligand structure, but the effects of ligand structure and electronic property of metal center on their catalytic performance remain underexplored. Herein, we designed and synthesized two pairs of isomeric tridentate β-ketoimine complexes TiL_a/TiL_b and TiL_c/TiL_d with methylthioaniline and methylthioethylamine side arms, respectively, which exhibited moderate to extremely high activity over 10⁶ g (mol Ti)⁻¹· h⁻¹·atm⁻¹ for the polymerization of ethylene and the copolymerization of ethylene with α-olefins (1-hexene, 1-octene) and polar comonomer (9-decen-1-ol) in the presence of MAO, with the catalytic activities in the order: TiL_d > TiL_c > TiL_a > TiL_b. The regioisomers TiL_c and TiL_d with methylthioethylamine side arm showed significantly higher activity for ethylene (co)polymerization than that of the isomeric TiL_a and TiL_b with methylthioaniline side arm, especially for ethylene copolymerization with α-olefins or polar comonomer 9-decen-1-ol, indicating an obvious positive “comonomer effect”. The complex TiL_d exhibited the highest ethylene (co)polymerization activity and comonomer insertion rate. Structural optimization using density functional theory (DFT) calculations suggested that the “side arms” and the electronic properties of titanium in β-ketoimine titanium complexes played a key role for ethylene polymerization and copolymerization.

This study focuses on the synthesis and characterization of Mn₂Sb₂O₇ and MnSb₂O₆ nanocatalysts, which were analyzed using Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), Brunauer-Emmet-Teller (BET) analysis, scanning electron microscopy with energy dispersive X-ray (SEM-EDS), and transmission electron microscopy (TEM). The results confirm that the catalysts have similar chemical compositions and structures, with small amounts of vanadium (V) or iron (Fe) dopants evenly distributed throughout the material. These nanocatalysts demonstrated high efficiency in the one-pot synthesis of 2-amino-4H-chromenes from malononitrile, dimedone, and aryl aldehydes, achieving yields of 66–90% under optimal conditions using 10 mg of catalyst in ethanol at room temperature. Due to their amphoteric nature, the catalysts enable reactions via acid-mediated or base-mediated Hann-Lapworth mechanisms. Under optimal conditions, the catalysts exhibited turnover numbers (TON) ranging from 1.8 to 3.6 and turnover frequencies (TOF) between 0.0005 and 0.0009 s⁻¹. Moreover, the catalysts can be recovered and reused without losing activity, making them valuable for sustainable chemical synthesis applications.

Five novel manganese (I) tricarbonyl complexes were synthesized by the reaction of Mn (CO)₅Br with quinoline-2-carboxaldehyde and different anilines. The IR, UV, and myoglobin results indicate that these complexes can be used as photoCORMs (photo photoinduced carbon monoxide releasing molecules) activated by red light. The visible range spectra display strong charge transfer (CT) bands, the maxima of which are sensitive to the ligand substituents. Density functional theory (DFT) and time-dependent density functional theory (TDDFT) computations show that these CT transitions are admixtures of metal-to-ligand and aniline-to-quinoline charge transfers and that increasing the electron-donating ability on the aniline functionality can lead to shifts in the absorption bands of the corresponding compounds to longer wavelengths and to enhanced band intensities, thus enhancing their photoactivity. Photolysis of these complexes in aerobic solution leads to CO photodissociation followed by oxidation of the Mn(I) center to Mn(II).

Substituted hydrazones and dihydrazones, as polydenatate ligand, reported high coordination chemical behavior towards numerous transition metals of different oxidation states for alternated applicable interest. Therefore, with a facile condensed reaction of the salicylaldehyde with tartric dihydrazide, a chelated tartrato-dihydrazone ligand (H₂Ltz) was formed. The coordinated features of H₂Ltz versus two divalent metal ions of Cu (II) and Ni (II) ions were assumed to form two new bimetallic-organic framework complexes, assigning triagonal bipyramidal and tetrahedral geometries (CuLtz and NiLtz, respectively). Their structural elucidating was determined within the analytical tools spectroscopically. The effectiveness of the growth inhibition for H₂Ltz, CuLtz, and NiLtz against six named bacterial and fungal series, and three human cancer cell lines were examined discovering the reactive role of two central M (II) ions in CuLtz and NiLtz, respectively. The binding character of H₂Ltz, CuLtz, and NiLtz, with calf thymus DNA, that is, DNA, was estimated based on the variation in viscometric/spectrophotometric features. The two bimetallic-chelates represented more distinguished inhibitive attitudes than the regarded one of H₂Ltz assigning to the inhibitive zones (mm) and the half-inhibited concentration (IC₅₀, μM) of growth inhibition of the studied microbes and human tumor cells, respectively. The examination of the binding action of H₂Ltz, CuLtz, and CuLtz with DNA was approved according to the enhanced viscosity and the electronic spectral changes. Also, binding constants (14.09, 15.09, and 16.12 $��\times �$ 10⁷ mol⁻¹ dm³), Gibb's free energy (−42.06, −45.23, and −46.41 kJ mol⁻¹), and the chromism (mainly hypo modes) are assigned to estimate the binding modes. Rewardingly, the bimetallic-chelates MLtz displayed modified binding action more than that of H₂Ltz against DNA regarding their hydrophobicity/lipophilicity.

Benzophenone is a versatile molecular scaffold that has been extensively explored in medicinal chemistry because of its propensity to exhibit a wide range of biological activities. This study represents a new azide (5) and triazole (6) compounds that were synthesized and well characterized by using FTIR, ¹H and ¹³C NMR spectroscopy and mass spectrometry. UV-vis and fluorescence spectroscopic studies identified the sensitivity of compound 6 towards Fe(III) with no substantial interference from other metal ions. LOD values for recognition of Fe(III) were found to be 7.94 × 10⁻⁵ and 3.67 × 10⁻⁷ M, respectively. The biological studies of the compounds (5 and 6) depicted the antibacterial activity against Bacillus subtilis, Staphylococcus aureus and Pseudomonas aeruginosa with the minimum inhibitory concentration range of antibiotics 0.12–6.2 mg/mL. Molecular docking experiments with various bacterial proteins demonstrated that compounds 5 and 6 possessed very low binding energies of −10.39 and −9.14 kcal mol⁻¹ respectively. Both the compounds showed excellent cytotoxic activities against HeLa cells (cervical cell line). Further, the antioxidant quality of compound 6 has been analysed.

Nano-sized tridentate transition metal(II) chelates, specifically [M(FONS)Cl] with H-FONS = ligand and M = Cu(II) (C1), Ni(II) (C2), Pd(II) (C3), and Pt(II) (C4), underwent synthesis and subsequent characterization. The HOMO–LUMO energy gaps (ΔE) were used to create theoretical models for the structure and confirmation barriers in molecular systems for the ligand (H-FONS) and metal chelates. It was found that the Cu(II), Ni(II), Pd(II), and Pt(II) chelates have lower values for HOMO–LUMO energy gaps (ΔE), indicating that they are more stable than the H-FONS 1igand.The metal formed four coordinated with the tridentate NOS donor Schiff base to form square-planar geometry chelates. The results of TEM, EDX, AFM, and x-ray diffraction calculations for the bivalent metal chelates indicated sharp and intense diffraction peaks, confirming their crystalline nature and nanoscale particle size. The interaction between calf thymus DNA (CT-DNA) and the chelates was examined utilizing the UV–Vis spectroscopic method, revealing their capacity to bind with CT-DNA via intercalation mode. Nano-sized metal(II) chelates show a higher viscous nature than H-FONS. The cytotoxicity of H-FONS and its metal(II) chelates in nano form against the liver cancer cell line (HepG2) was evaluated by studying in vitro cell proliferation using the MTT assay. The findings demonstrated that all compounds exhibited anticancer properties, displaying a dose-dependent response. Our flow cytometry data indicate significant levels of cell cycle arrest in the liver cancer cell line. By molecular docking study, it was found that the Cu(II) chelate (C1) showed the highest and better binding affinity (−8.2 and −8.7 kcal/mol) than other 1igand (H-FONS) and comp1exes (C2–C4) for the BCL2 and PBP3 proteins central activities.