Dithiocarbamate Ligands Research Articles

Synthesis, Characterisation and Biological Activity of New Co, Ni, Zn and Cd Polymeric Complexes Derived from Dithiocarbamate Ligand

Synthesis, Characterisation and Biological Activity of New Co, Ni, Zn and Cd Polymeric Complexes Derived from Dithiocarbamate Ligand

Biological and theoretical investigation of cyclohexylamine dithiocarbamate metal (II) complexes

AbstractA series of metal (II) complexes of N‐cyclohexyl amine dithiocarbamate ligand are synthesized and characterized by Fourier transform infrared, 1H, 13C NMR, mass spectroscopy, and elemental analysis. The surface structural pattern of the prepared complexes were investigated by scanning electron microscope and X‐ray diffraction techniques. The prepared complexes possessed crystalline characteristic with size average ranging from 16 to 30 nm. Moreover, the biological activity of the synthesized complexes were tested against Klebsiella pneumoniae, Escherichia coli, and Staphylococcus aureus. Among the prepared complexes, copper (II) complex displayed the highest activity. In addition, molecular docking study was performed against bacterial tyrosinase enzyme which showed good binding interactions and is in agreement with the experimental findings. Furthermore, the in silico toxicity studies reveal that the complexes are mostly non‐irritant with mild toxicity. Different quantum parameters including electron affinity, ionization energy, dipole moment, hardness and vibrational frequencies were calculated for the ligand and its complexes using Gaussian 09 program and B3LYP/SDD level of theory.

Dithiocarbamate ligands as heavy metal expectorants from aqueous solutions

The uncontrolled concentrations of heavy metals introduced into the water sources need an effective method for their removal. The dithiocarbamate (dtc) ligands are the most popular precipitating agents used for the removal of metals from wastewater. Presently, two novel dtc ligands, one without methylene linker (K2L1) and the other with methylene linker (K2L2) were used for the removal of eight heavy metals ions including Fe2+, Co2+, Ni2+, Cu2+, Cd2+, Ag+, Zn2+ and Pb2+ from the aqueous solution. These dtc ligands contain acyl (NH-C = O) and S, S (thiolate) functional groups. The results indicated that the metal removal efficiency of both ligands was almost 100% at pH 4 and 7 and free of the linker effect and acyl functional groups but depends on the S, S binding sites. It exhibited a distinct selectivity for the removal of metal ions (Pb2+ ∼ Cu2+ ∼ Ag1+ > Cd2+ > Co2+ > Ni2+ > Zn2+ > Fe2+). The developed methods have the potential for the removal of heavy metals and can be used for other thiophilic metals that are water-soluble. HIGHLIGHTS Water treatment, contaminated by heavy metal ions. Synthesis and characterization of two novel dithiocarbamate ligands. Effect of methylene (-CH2-) linker of dithiocarbamtes on heavy metals extraction. pH and temperature effect on the extraction efficiency of ligands.

Synthesis, characterization, and in vitro antibacterial and cytotoxic study of Co(II), Ni(II), Cu(II), and Zn(II) complexes of N-(4-methoxybenzyl) N-(phenylethyl) dithiocarbamate ligand

Four new homoleptic complexes of Co(II) [C-1], Ni(II) [C-2], Cu(II) [C-3], and Zn(II) [C-4] derived from N-(4-methoxybenzyl) N-(phenylethyl) dithiocarbamate ligand (KL) with general formula ML2 were synthesized with good yield and characterized by elemental analysis and different spectroscopic techniques like FTIR, 1H and 13C NMR, HRMS, UV–vis and fluorescence spectroscopy. The crystal structure of the complex C-4 was determined by the single crystal X-ray diffraction technique (SC-XRD), which shows a distorted square pyramidal geometry around the Zn(II) ion. Thermogravimetric studies of all four complexes were performed and found that decomposition occurred in three steps and the final product of the thermal decomposition was metal sulfides. The magnetic properties of cobalt, nickel, and copper complexes were analyzed by a vibrating sample magnetometer (VSM) and the hysteresis of magnetization showed the paramagnetic nature of cobalt and copper complexes while the diamagnetic nature of the nickel complex. Electronic spectral studies of the ligand and all four complexes were recorded in methanolic solution and the spectra show the absorption for the ligand at 301 nm and the absorption band for complexes was observed in the range 265-275 nm which is due to intra-ligand charge transfer (ILCT) transitions. Complexes C-1, C-2, and C-3 showed transitions in the range of 325-445 nm due to ligand-to-metal charge transfer (LMCT) transitions. Anti-bacterial studies of all compounds were performed against Bacillus subtilis, Staphylococcus aureus, Clostridium sporogenes, and Escherichia coli and the result showed that complexes C-2 and C-4 have significant anti-bacterial properties. The cytotoxicity study of all compounds against breast cancer cell line MCF-7 shows that complex C-2 has a potential anti-cancerous property with the least IC50 value against normal cell line HEK-293.

Series of Organotin(IV) Compounds with Different Dithiocarbamate Ligands Induced Cytotoxicity, Apoptosis and Cell Cycle Arrest on Jurkat E6.1, T Acute Lymphoblastic Leukemia Cells.

The discovery of cisplatin has influenced scientists to study the anticancer properties of other metal complexes. Organotin(IV) dithiocarbamate compounds are gaining attention as anticancer agents due to their potent cytotoxic properties on cancer cells. In this study, a series of organotin compounds were assessed for their toxic effects on the Jurkat E6.1 cell line. WST-1 assay was used to determine the cytotoxic effect of the compounds and showed that six out of seven organotin(IV) dithiocarbamate compounds exhibited potent cytotoxic effects toward T-lymphoblastic leukemia cells, Jurkat E6.1 with the concentration of IC50 ranging from 0.67-0.94 µM. The apoptosis assay by Annexin V-FITC/PI staining showed that all tested compounds induced cell death mainly via apoptosis. Cell cycle analysis assessed using RNase/PI staining showed that organotin(IV) dithiocarbamate compounds induced cell cycle arrest at different phases. In conclusion, the tested organotin(IV) dithiocarbamate compounds demonstrated potent cytotoxicity against Jurkat E6.1 cells via apoptosis and cell cycle arrest at low IC50 value. However, further studies on the mechanisms of action are required to probe the possible potential of these compounds on leukemia cells before they can be developed into anti-leukemic agents.

Reactivity of a Dithiocarbamate-Ligated [WVI≡S] Complex with Hydride Donors: Toward a Synthetic Mimic of Formate Dehydrogenase.

Formate dehydrogenase (FDH) enzymes catalyze redox interconversion of CO2 and HCO2-, with a key mechanistic step being the transfer of H- from HCO2- to an oxidized active site featuring a [MVI≡S] group in a sulfur-rich environment (M = Mo or W). Here, we report reactivity studies with HCO2- and other reducing agents of a synthetic [WVI≡S] model complex ligated by dithiocarbamate (dtc) ligands. Reactions of [WVIS(dtc)3][BF4] (1) conducted in MeOH solvent generated [WVIS(S2)(dtc)2] (2) and [WVS(μ-S)(dtc)]2 (3) products by a solvolysis pathway that was accelerated by the presence of [Me4N][HCO2] but did not require it. Under MeOH-free conditions, the reaction of 1 with [Et4N][HCO2] produced some [WIV(μ-S)(μ-dtc)(dtc)]2 (4), but predominantly [WV(dtc)4]+ (5), along with stoichiometric CO2 detected by headspace gas chromatography (GC) analysis. Stronger hydride sources such as K-selectride generated the more reduced analogue, 4, exclusively. The reaction of 1 with the electron donor, CoCp2, also produced 4 and 5 in varying amounts depending on reaction conditions. These results indicate that formates and borohydrides act as electron donors rather than hydride donors toward 1, an outcome that diverges from the behavior of FDHs. The difference is ascribed to the more oxidizing potential of [WVI≡S] complex 1 when supported by monoanionic dtc ligands that allows electron transfer to outcompete hydride transfer, as compared to the more reduced [MVI≡S] active sites supported by dianionic pyranopterindithiolate ligands in FDHs.

New anticancer potential Pt complex with tertamyl dithiocarbamate ligand: Synthesis, DNA targeting behavior, molecular dynamic, and biological activity

In this research, a new platinum complex, [Pt(phen)(tertamyl.dtc)]NO3, where (phen) is 1,10-phenanthroline and (tertamyl.dtc) is the tertamyl-dithiocarbamate ligand, has been synthesized and specified by UV–Vis, FT-IR, 1H NMR, and 13C NMR spectroscopies. Various spectroscopy methods and simulation studies studied DNA binding properties of the Pt dithiocarbamate derivative. UV–vis spectroscopic data and thermal stability study displayed the amount of groove binding between [Pt(phen)(tertamyl.dtc)]NO3 complex and CT-DNA. The results of fluorescence and CD studies demonstrated that [Pt(phen)(tertamyl.dtc)]NO3 binds on DNA as a groove binder, and the tendency to interact with DNA was measured by molecular docking simulation. Finally, different thermodynamic and binding parameters showed a spontaneous process, and hydrophobic forces were recognized as the main forces. The results and the simulation insights, showed that [Pt(phen)(tertamyl.dtc)]NO3 could bind to DNA and, via minor groove binding on G and T centers on DNA, formed a stable DNA complex. In vitro cytotoxicity was assessed in several human cell lines. Because of phenanthroline presence in the structure of the Pt complex, IC50 values of this complex against Panc1 and HT29 cell lines were obtained less than oxaliplatin and against HCT116 and MCF7 more than it.

Synthesis, characterization, molecular docking studies of Mn(II)Prolinedithiocarbamate and its potential as anticancer agents.

Breast cancer is a non-communicable disease but dangerous for women, and research on anti-breast cancer drug compounds is being investigated. Mn(II)Prolinedithiocarbamate (MnProDtc) complex was synthesized and characterized in cytotoxicity and in silico assay by molecular docking. Dithiocarbamate ligand plays an important role as an anticancer agent. Melting point determination, conductivity, UV-Vis spectroscopy, FT-IR spectroscopy, XRD, and HOMO-LUMO have been studied. The binding of MnProDtc to cancer cells was examined by molecular docking, showing that the active sites of the MCF-7 strain, namely the protein O(6)-methylguanine-DNA methyltransferase (MGMT), caspase-8, and the estrogen receptor, bind to the complex. The results of the cytotoxic test of MCF-7 cancer cells undergoing apoptosis at a concentration of 37.50μg/ml with an IC50 value of 453.96μg/ml showed moderate anticancer activity in MCF-7 cancer cells.

Cd(II) and Pd(II) Mixed Ligand Complexes of Dithiocarbamate and Tertiary Phosphine Ligands-Spectroscopic, Anti-Microbial, and Computational Studies.

Mixed ligand complexes of Pd(II) and Cd(II) with N-picolyl-amine dithiocarbamate (PAC-dtc) as primary ligand and tertiary phosphine ligand as secondary ligands have been synthesized and characterized via elemental analysis, molar conductance, NMR (1H and 31P), and IR techniques. The PAC-dtc ligand displayed in a monodentate fashion via sulfur atom whereas diphosphine ligands coordinated as a bidentate mode to afford a square planner around the Pd(II) ion or tetrahedral around the Cd(II) ion. Except for complexes [Cd(PAC-dtc)2(dppe)] and [Cd(PAC-dtc)2(PPh3)2], the prepared complexes showed significant antimicrobial activity when evaluated against Staphylococcus aureus, Pseudomonas aeruginosa, Candida albicans and Aspergillus niger. Moreover, DFT calculations were performed to investigate three complexes {[Pd(PAC-dtc)2(dppe)](1), [Cd(PAC-dtc)2(dppe)](2), [Cd(PAC-dtc)2(PPh3)2](7)}, and their quantum parameters were evaluated using the Gaussian 09 program at the B3LYP/Lanl2dz theoretical level. The optimized structures of the three complexes were square planar and tetrahedral geometry. The calculated bond lengths and bond angles showed a slightly distorted tetrahedral geometry for [Cd(PAC-dtc)2(dppe)](2) compared to [Cd(PAC-dtc)2(PPh3)2](7) due to the ring constrain in the dppe ligand. Moreover, the [Pd(PAC-dtc)2(dppe)](1) complex showed higher stability compared to Cd(2) and Cd(7) complexes which can be attributed to the higher back-donation of Pd(1) complex.

Centrosymmetric Nickel(II) Complexes Derived from Bis-(Dithiocarbamato)piperazine with 1,1′-Bis-(Diphenylphosphino)ferrocene and 1,2-Bis-(Diphenylphosphino)ethane as Ancillary Ligands: Syntheses, Crystal Structure and Computational Studies

Two Ni(II) complexes with the formula [{Ni(dppf)}2{(L1)2}](PF6)2 (Ni-I) and [{Ni(dppe)}2{(L1)2}](PF6)2 (Ni-II) were prepared by reacting [Ni(dppf)Cl2] and [Ni(dppe)Cl2] (dppf = 1,1′-Bis-(diphenylphosphino)ferrocene; dppe = 1,2-Bis-(diphenylphosphino)ethane) with secondary amine piperazine derived ligand disodium bis-(dithiocarbamate)piperazine ((piper(dtc)2 = L1) and counter anion PF6−. These complexes were characterized by elemental analyses, FT-IR, 1H, 13C and 31P NMR, UV-Vis. spectroscopy and single crystal X-ray diffraction. The X-ray analyses reveal centrosymmetric structures where each Ni(II) centre adopts distorted square planar geometry defined by two sulfur centres of dithiocarbamate ligand and two phosphorus centres of dppf and dppe ligands in Ni-I and Ni-II, respectively. The supramolecular framework of both Ni-I and Ni-II are sustained by C-H⋯π and C-H⋯F interactions, and they also display interesting intramolecular C-H⋯Ni anagostic interactions. Further, the nature of these interactions are studied using Hirshfeld surface analyses, DFT and quantum theory of atoms in molecules (QTAIM) calculations. Additionally, non-covalent interaction (NCI) plot analyses were conducted to gain additional insight into these non-covalent interactions. This work is vital in a new approach towards the rational designing of the centrosymmetric molecules with interesting architectures.

SYNTHESIS AND CHARACTERIZATION OF BIS (DITHIOCARBAMATES) WITH NICKEL(II) AND COPER(II) METALS

Nickel (II) and Coper (II) dithiocarbamate complexes of general of fomula M (Rdtc) 2. The present paper describes the Synthesis and spectral properties of similar complexes of the following new dithiocarbamate ligands, cyclohexyldithiocarbamate (Chex Dtc), dicyclohexyldithiocarbamate (DchexDtc). The Complexes have been characterized on the basis of analytical data magneto chemical, conductivity measurements, electronic and infrared spectroscopies as square planar Nickel (II), Coper (II) compounds. The Result of the spectroscopic studies indicates that the dithiocarbamate ligand is always bidentate.
 All the complexes are non-conducting in DMF solution

A heteroleptic fused bi-cuboctahedral Cu21S2 cluster.

A new dicationic cluster, [Cu21S2{S2CNnBu2}9(C2Ph)6]2+, where the Cu21S2 kernel consists of two S@Cu12 cuboctahedra sharing a triangular Cu3 face is reported. Its waist part is bridged by three dithiocarbamate ligands, each in a hexaconnective, hexametallic (μ3, μ3) coordination pattern, an unprecedented feature in Cu nanocluster chemistry.

Synthesis, spectral, structural and DFT studies on Tl(III) dithiocarbamate complexes: Preparation of Tl2S nanoparticles from tris(N-benzyl-N-furfuryldithiocarbamato-S,S’)thallium(III)

Tris(N,N-difurfuryldithiocarbamato-S,S’)thallium(III) (1), tris(N-benzyl-N-furfuryldithiocarbamato-S,S’)thallium(III) (2) and tris(N-furfuryl-N-(2-phenylethyl)dithiocarbamato-S,S’)thallium(III) (3) have been prepared and characterized by elemental analysis, IR and NMR (1H and 13C) spectroscopy. Single crystal X-ray structural analysis was carried out for 1. X-ray crystallography revealed that complex 1 is monomer. Thallium is hexacoordinated with six sulfur atoms from three chelating N,N-difurfuryl dithiocarbamate ligands in a distorted octahedral geometry. Complex 1 is further stabilized by various interactions such as CH…π (chelate), CH…π, CH…S and CH…O interactions. CH…O interactions lead to the formation of 18 membered macrocyclic ring. Hirshfeld surface analysis (dnorm surface and 2-D fingerprint plots) were performed using Crystal explorer 3.1 program. The major contributions for the crystal packing are from H…H, S…H/H…S, O…H/H…O and C…H/H…C interactions. Molecular optimization, molecular electrostatic potential and frontier molecular orbitals were calculated using DFT method for 1. DFT calculations on 1 revealed that HOMO was localized predominantly over furfuryl ring carbon atoms, whilst the LUMO was located on Tl and S atoms, with the HOMO-LUMO energy gap being 2.5067 eV. Thallium sulfide nanoparticles Tl2S-1 and Tl2S-2 have been prepared from complex 2 using conventional heating and microwave irradiation, respectively. The as-prepared Tl2S nanoparticles have been characterized by PXRD, EDS, HR-TEM, UV–vis absorption and fluorescence spectroscopy. The X-ray diffraction pattern confirms the rhombohedral phase of as-prepared Tl2S.

LASER-INDUCED MODIFICATION ON SOME PROPERTIES OF PREPARED Cu(II) COMPLEXES

Two complexes - derived from dithiocarbamate ligand (L) and their adduct with nitrogen base of the general formula [Cu(L)2], [Cu(L)2(A)] obtained by the condensation of CuCl2.2H2O with L= diisopropyl amine dithiocarbamate and A=1,10-phenanthroline weve directly been synthesized and characterized by infrared spectra, metal content and magnetic measurement. Some properties of these two complexes, including UV/VIS absorption, melting point, and molar conductivity measurement are characterized in both cases before and after applying laser diode radiation with an emission wavelength of 532 nm. It found that laser has potential effects on Cu complexes under investigation for specific conditions and doses where new complexes have been observed, and spectral data and magnetic measurement showed a tetrahedral and octahedral geometries for [Cu(L)2] and[Cu(L)2(A)], respectively.

Addressing the gaps in homeostatic mechanisms of copper and copper dithiocarbamate complexes in cancer therapy: a shift from classical platinum-drug mechanisms.

The platinum drug, cisplatin, is considered as among the most successful medications in cancer treatment. However, due to its inherent toxicity and resistance limitations, research into other metal-based non-platinum anticancer medications with diverse mechanisms of action remains an active field. In this regard, copper complexes feature among non-platinum compounds which have shown promising potential as effective anticancer drugs. Moreover, the interesting discovery that cancer cells can alter their copper homeostatic processes to develop resistance to platinum-based treatments leads to suggestions that some copper compounds can indeed re-sensitize cancer cells to these drugs. In this work, we review copper and copper complexes bearing dithiocarbamate ligands which have shown promising results as anticancer agents. Dithiocarbamate ligands act as effective ionophores to convey the complexes of interest into cells thereby influencing the metal homeostatic balance and inducing apoptosis through various mechanisms. We focus on copper homeostasis in mammalian cells and on our current understanding of copper dysregulation in cancer and recent therapeutic breakthroughs using copper coordination complexes as anticancer drugs. We also discuss the molecular foundation of the mechanisms underlying their anticancer action. The opportunities that exist in research for these compounds and their potential as anticancer agents, especially when coupled with ligands such as dithiocarbamates, are also reviewed.

Synthesis, spectroscopic characterization, biological activity, and conducting properties of functionalized Ni(II) dithiocarbamate complexes with solvent extraction studies of the ligands

A series of new nickel(II) dithiocarbamate complexes of general formula [M L2], (where L = benzyl(4-fluorobenzyl)carbamodithioate (L1), benzyl(4-cyanobenzyl)carbamodithioate (L2), ethyl(4-methylbenzyl)carbamodithioate (L3), (4-methoxybenzyl) (naphthalen-1-ylmethyl)carbamodithioate (L4) and ethyl(4-methoxybenzyl)carbamodithioate (L5)) have been synthesized, and characterized via elemental analysis, FT-IR, electronic spectra, 1H NMR, 13C NMR, Mass spectrometry and Thermogravimetric analysis (TGA). The continuous variation method (Job's method) was used to determine the stoichiometry of the complexes. TGA was used to analyze the thermal decomposition behavior of metal complexes in nitrogen atmosphere. As a result of the thermal decomposition process, all of the complexes produced NiS as the final product. X-ray Diffraction (XRD), Energy dispersive X-ray analysis (EDAX), and Transmission electron microscopy (TEM) studies confirm the formation of NiS nanomaterial. Crystalline size of NiS was obtained between 19.97 to 21.35 nm range by applying the Scherrer equation using XRD. Solid-state electrical conductivities reveal that all the complexes behave as a semiconductor at room temperature. All the synthesized dithiocarbamate ligands and complexes were screened against five human bacterial pathogens (Escherichia coli, Staphylococcus aureus, Salmonella typhi, Aeromonas hydrophila, and Shigella boydii) by disc diffusion method. Solvent extraction studies show that the ligand has strong extractability towards metal ions in a basic medium (pH = 10).

Synthesis, spectral, crystal structure, DFT and Hirshfeld surface analysis of Zn(II) complexes involving dithiocarbamate and imine ligands and usage as precursor to prepare ZnS for photodegradation of dyes

Three new zinc(II) complexes, bis(N-(2-phenylethyl)-N-(thiophen-2-ylmethyl)dithiocarbamato-S,S’)zinc(II) (1), bis(N-(2-phenylethyl)-N-(thiophen-2-ylmethyl)dithiocarbamato-S,S’)(pyridine)zinc(II) (2) and (2,2’bipyridine)bis(N-(2-phenylethyl)-N-(thiophen-2-ylmethyl)dithiocarbamato-S,S’)zinc(II) (3) were synthesized. All the complexes were characterized by 1H and 13C NMR and IR spectroscopy, together with elemental analysis. The crystal structures of 2 and 3 were determined by X-ray crystallography, which describe a distorted square pyramidal and distorted octahedral coordination environment around the Zn(II) ion in 2 and 3, respectively. One of the interesting structural features of 2 is the unusual intermolecular C-H…Zn interaction. The optimized structures of 1-3 were obtained using density functional theory at the B3LYP level. Hirshfeld surface analysis and two dimensional finger print plots were examined to study the contributions of the various intermolecular contacts within the supramolecular structure and zinc sulfide nanoparticles were prepared from 1 and 2 characterized using powder X-ray diffraction, scanning electron microscopy, Energy dispersive X-ray spectroscopy and UV-vis diffused reflectance spectroscopy. The PXRD data reveal that the zinc sulfide nanoparticles possess wurtzite structure. The photocatalytic activity of zinc sulfide prepared from 1 was studied by degrading methylene blue and rhodamine-6G in aqueous medium under UV irradiation as a function of time. This study indicates the high catalytic activity of as-prepared ZnS from 1.

Spectroscopic, computational, anti-bacterial studies of bivalent metal complexes of N-picolyl-amine dithiocarbamate

This study reports the synthesis of seven picolylamine dithiocarbamate complexes of M(II) {M =CoII (1), NiII (2), CuII (3), PdII (4), ZnII (5), CdII (6) and HgII (7)}. CHN analysis, conductivity measurements, magnetic susceptibility measurement, FT-IR, 1H and 13C-NMR, SEM, and XRD were used to investigate the structural geometries of the complexes. The dithiocarbamate ligand coordinates to the M(II) ion in a bidentate mode through sulfur atoms forming a square planar or tetrahedral geometry. Moreover, the surface structural analysis revealed nano-pattern properties. For instance, complexes of Cd(II) and Hg(II) showed a nano-flower pattern, averaging 2–5 µm. Furthermore, the obtained complexes exhibited biological activity properties. The results showed that the new metal (II) compounds possessed remarkable antibacterial inhibition activity against both Gram-positive and Gram-negative bacteria. Additionally, the complexes [Ni(PA-dtc)2], [Cu(PA-dtc)2], and [Pd(PA-dtc)2] were theoretically studied and their quantum parameters were evaluated using Gaussian 09 program at B3LYP/SDD level of theory. The optimized structures of all of the three complexes showed square planar geometry. The calculated bond lengths showed close values, specifically for CSS and CN group, which suggests a partially double bond character. Other quantum parameters have evaluated and showed similar properties such as the total energy, HOMO-LUMO energy gap, Affinity, Hardness, and dipole moment.

Magnetic MCR-Functionalized Graphene Oxide Complexed with Copper Nano-Particles: An Efficient and Recyclable Nanocatalyst for Ullmann C–N Coupling Reaction

In this study, we report the synthesis of Cu nanoparticle modified dithiocarbamate (DTC)-functionalized magnetic graphene oxide (GO) nanocatalyst through a one-pot three component reaction. It has an excellent affinity for copper nanoparticles due to its DTC ligand amide motif. The structure of the synthesized catalysts was confirmed by using FT-IR, TGA, CHNS, SEM, XRD, EDS mapping, and ICP. The catalytic activity of the synthesized nanocatalyst was investigated in Ullmann cross-coupling reaction for the synthesis of N-aryl amines, which resulted in high reaction yields, easy workup, and short reaction times. The catalyst is separated easily by a magnetic field and can be reused for at least five successive runs without significant loss of catalytic activity. The nature of the supported DTC on the GO’s surface improved the catalytic activity of the graphene, provided homogeneity to the catalyst, and enhanced the capability of coordination with copper ions. Facile catalyst recovery and reusability, simple setup procedure, generality of the method and high turnover number (TON) make this procedure an environmentally benign approach for preparing the titled compounds. Based on the findings of this study, it appears that the catalytic system introduced can be used to prepare other beneficial heterocyclic compounds.

Synthesis, crystal structure, DFT and Hirshfeld surface analysis of Ni(II) complexes: Precursor for nickel sulfide nanoparticles

Homoleptic complexes, [Ni(iprbpedtc)2] (1) and [Ni(fbtfdtc)2](2) were prepared. Furthermore, 1 and 2 were used as synthon to prepare heteroleptic complexes, [Ni(iprbpedtc)(NCS)(PPh3)] (3) and [Ni(fbtfdtc)(NCS)(PPh3)](4) (where iprbpedtc is N-(4-isopropylbenzyl)-N-(2-phenylethyl)dithiocarbamate and fbtfdtc is N-(4-fluorobenzyl)-N-((tetrahydrofuran-2-yl)methyl)dithiocarbamate). The resulting complexes were characterized by elemental analysis, Fourier transform infrared, NMR (1H and 13C) and electronic spectroscopic techniques. The crystal structures of complexes 1, 3 and 4 were determined by single crystal X-ray diffraction and show that the dithiocarbamate ligands are coordinated to the nickel atom in the bidentate manner and the central atom is four coordinated. Hirshfeld surface analysis 1, 3 and 4 reveal that H…H interactions are the largest contribution in the molecular packing. In addition, the structures of 1, 3 and 4 were analyzed with DFT-based approaches. The analysis of the electrophilicity index indicates that complex 4 has the greater electrophilic character compared to those of 1 and 3. The catalytic activity of nanoparticles was evaluated for the degradation of rhodamine-6G dye. Complex 2 was used as a precursor for the preparation of nickel sulfide nanoparticles. Its morphology, structure and optical properties were evaluated using powder X-ray diffraction, scanning electron microscopy, energy dispersive X-ray spectroscopy and UV-Vis diffuse reflectance spectroscopy. PXRD study shows that the as-prepared nanoparticles consist of β-NiS and α-Ni22.52S19.44. EDS analysis confirms the formation nickel sulfide.