Coordination of a triazine ligand with CuII and AgI investigated by spectral,structural, theoretical and docking studies

Two complexes of 5‐phenyl‐3‐(pyridin‐2‐yl)‐1,2,4‐triazine (PPTA), namely (ethanol‐κO)bis(nitrato‐κO)[5‐phenyl‐3‐(pyridin‐2‐yl‐κN)‐1,2,4‐triazine‐κN²]copper(II), [Cu(NO₃)₂(C₁₄H₁₀N₄)(C₂H₆O)] or [Cu(NO₃)₂(PPTA)(EtOH)] ( 1 ), and bis[μ‐5‐phenyl‐3‐(pyridin‐2‐yl)‐1,2,4‐triazine]‐κ³N¹:N²,N³;κ³N²,N³:N¹‐bis[(nitrato‐κO)silver(I)], [Ag₂(NO₃)₂(C₁₄H₁₀N₄)₂] or [Ag₂(NO₃)₂(μ‐PPTA)₂] ( 2 ), were prepared and characterized by elemental analysis, FT–IR spectroscopy and single‐crystal X‐ray diffraction. The X‐ray structure analysis of 1 revealed a copper complex with square‐pyramdial geometry containing two O‐donor nitrate ligands along with an N,N′‐donor PPTA ligand and one O‐donor ethanol ligand. In the binuclear structure of 2 , formed by the bridging of two PPTA ligands, each Ag atom has an AgN₃O environment and square‐planar geometry. In addition to the four dative interactions, each Ag atom interacts with two O atoms of two nitrate ligands on adjacent complexes to complete a pseudo‐octahedral geometry. Density functional theory (DFT) calculations revealed that the geometry around the Cu and Ag atoms in 1 ^opt and 2 ^opt (opt is optimized) for an isolated molecule is the same as the experimental results. In 1 , O—H…O hydrogen bonds form R₁²(4) motifs. In the crystal network of the complexes, in addition to the hydrogen bonds, there are π–π stacking interactions between the aromatic rings (phenyl, pyridine and triazine) of the ligands on adjacent complexes. The ability of the ligand and complexes 1 and 2 to interact with ten selected biomacromolecules (BRAF kinase, CatB, DNA gyrase, HDAC7, rHA, RNR, TrxR, TS, Top II and B‐DNA) was investigated by docking studies. The results show that the studied compounds can interact with proteins better than doxorubicin (except for TrxR and Top II).     

Synthesis,crystal structures,photoluminescence, electrochemistry and DFT study of aluminium(III) and gallium(III) complexes containing a novel tetradentate Schiff base ligand

Single crystals of the aluminium and gallium complexes of 6,6′‐{(1E,1′E)‐[1,2‐phenylenebis(azanylylidene)]bis(methanylylidene)}bis(2‐methoxyphenol), namely diaqua(6,6′‐{(1E,1′E)‐[1,2‐phenylenebis(azanylylidene)]bis(methanylylidene)}bis(2‐methoxyphenolato)‐κ⁴O¹,N,N′,O^1′)aluminium(III) nitrate ethanol monosolvate, [Al(C₂₂H₁₈N₂O₄)(H₂O)₂]NO₃·C₂H₅OH, 1 , and diaqua(6,6′‐{(1E,1′E)‐[1,2‐phenylenebis(azanylylidene)]bis(methanylylidene)}bis(2‐methoxyphenolato)‐κ⁴O¹,N,N′,O^1′)gallium(III) nitrate ethanol monosolvate, [Ga(C₂₂H₁₈N₂O₄)(H₂O)₂]NO₃·C₂H₅OH, 2 , were obtained after successful synthesis in ethanol. Both complexes crystallized in the triclinic space group P, with two molecules in the asymmetric unit. In both structures, in one of the independent molecules the tetradentate ligand is almost planar while in the other independent molecule the ligand shows significant distortions from planarity, as illustrated by the largest distance from the plane constructed through the central metal atom and the O,N,N′,O′‐coordinating atoms of the ligand in 1 of 1.155 (3) Å and a distance of 1.1707 (3) Å in 2 . The possible reason for this is that there are various strong π‐interactions in the structures. This was confirmed by density functional theory (DFT) calculations, as were the other crystallographic data. DFT was also used to predict the outcome of cyclic voltammetry experiments. Ligand oxidation is more stabilized in the gallium complex. Solid‐state photoluminescence gave an 80 nm red‐shifted spectrum for the gallium complex, whereas the aluminium complex maintains the ligand curve with a smaller red shift of 40 nm.     

Coordination polymers of CdII and PbII with croconate show remarkable differences in coordination patterns: a structural and spectroscopic study

The croconate dianion is a highly versatile ligand with two tautomeric forms making it useful for building large superstructures in the solid state. The single‐crystal X‐ray structures of Pb^II– and Cd^II–croconate coordination polymers, namely catena‐poly[[[diaqualead(II)]‐μ‐croconato‐κ⁴O¹,O²:O³,O⁴] monohydrate], {[Pb(C₅O₅)(H₂O)₂]·H₂O}_n, 1 , and catena‐poly[[triaquacadmium(II)]‐μ‐croconato‐κ⁴O¹,O²:O³,O⁴], [Cd(C₅O₅)(H₂O)₃]_n, 2 , have been determined. Both polymers form one‐dimensional (1D) structures; 1 is a nonplanar 1D zigzag coordination polymer extended along the crystallographic b axis, whereas 2 is a planar 1D ribbon parallel to the [101] direction. In 2 , three H₂O molecules are coordinated directly to the metal atom, while in 1 , only two H₂O molecules are directly coordinated to the metal atom. A third interstitial H₂O molecule is involved in hydrogen bonding with O atoms of the croconate ligands of an adjacent layer and other H₂O molecules, resulting in stacked double layers parallel to the [105] plane. Solid‐state FT–IR and solution UV–Vis spectra also substantiate the croconate coordination.     

Arene ruthenium complexes incorporating immine/azine hybrid-chelating N-N donor ligands: synthetic, spectral, structural aspects and DFT studies

New series of mono and binuclear arene ruthenium complexes [{(η⁶-arene)RuCl(L)}]⁺ and [{(η⁶-arene)RuCl}₂(μ-L)₂]²⁺ (arene=benzene, p-cymene or hexamethylbenzene), {L=pyridine-2-carbaldehyde azine (paa), p-phenylene-bis(picoline)-aldimine (pbp) and p-bi-phenylene-bis(picoline)-aldimine (bbp)} are reported. The complexes have been fully characterized and molecular structure of the representative mononuclear complex [(η⁶-C₆Me₆)RuCl(paa)]BF₄ (1), binuclear complexes [{(η⁶-C₁₀H₁₄)RuCl}₂(μ-paa)](BF₄)₂ (3) and [{(η⁶-C₁₀H₁₄)RuCl}₂(μ-pbp)](BF₄)₂ (6) have been determined by single crystal X-ray diffraction analyses. Single crystal X-ray structure determination revealed that in the binuclear complexes the [(η⁶-C₁₀H₁₄)RuCl]⁺ units are trans disposed. Further, the crystal packing in the complexes 1, 3 and 6 is stabilized by C-H?X type (X=Cl, F) inter, intramolecular hydrogen bonding and π-π stacking (3). To explore the ambiguous nature of the bonding between pyridine-2-carbaldehyde azine (paa) with ruthenium containing units [(η⁶-arene)RuCl]⁺, DFT/B3LYP calculations have been performed on the complexes [(η⁶-arene)RuCl(paa)]⁺ (arene=C₆H₆, I; C₆Me₆, II; C₁₀H₁₄, III).     

Theoretical investigation on molecular structure of a new mononuclear copper(II) thiocyanato complex with tridentate Schiff base ligand

An asymmetrical Schiff base ligand, 4-bromo-2-(2-pyridylmethyliminomethyl)phenol (HL), and its copper(II) complex, [Cu(L)SCN] (1), have been synthesized. Complex 1 is experimentally characterized by elemental analysis, FT-IR and UV–vis spectroscopic techniques, and cyclic voltammetry. The structure of the complex has been established by single-crystal X-ray diffraction studies, which reveal a square planar geometry of the central copper(II) ion in 1. The neighboring molecules of the complex connect each other by π–π stacking interactions with centroid-to-centroid ring distance 3.653 Å. The ligand can display two possible tautomeric forms; therefore, 1 can have an alternate molecular structure. DFT calculations have been employed to investigate the structure and relative stabilities of the suggested tautomeric forms of the ligand and its corresponding copper(II) complex.     

A study of structural effects on linear and nonlinear response of bicompartmental Ni (II) Schiff base complexes

Herein we investigate imaginary third order NLO activity, optical limiting capability and first hyperpolarizabilities of five Ni (II) salen complexes using experimental and theoretical methods. The complexes are tuned to have different NLO response by changing mainly the diimine spacer group. Out of the compounds reported, the one with o‐phenylene spacer group exhibits the highest NLO activity comparable with that of polymers and semiconductors which is followed by the compound with ethylene spacer unit. The order of activity is a direct function of the degree of π‐delocalization. Further all the tested compounds returned outstanding optical limiting capabilities making them excellent materials for fabrication of such devices. The experimental results were substantiated with frontier orbital calculations carried out using DFT at M06/6‐31G* level of theory and complex with aromatic spacer group exhibits least energy gap and highest activity. The total dipole moment, polarizability and first hyperpolarizability were also calculated at the same level of theory which are also in line with the experimentally observed results.     

Chemistry of transition‐metal complexes containing functionalized phosphines: synthesis and structural analysis of rhodium(I) complexes containing allyl and cyanoalkylphosphines

A series of related acetylacetonate–carbonyl–rhodium compounds substituted by functionalized phosphines has been prepared in good to excellent yields by the reaction of [Rh(acac)(CO)₂] (acac is acetylacetonate) with the corresponding allyl‐, cyanomethyl‐ or cyanoethyl‐substituted phosphines. All compounds were fully characterized by ³¹P, ¹H, ¹³C NMR and IR spectroscopy. The X‐ray structures of (acetylacetonato‐κ²O,O′)(tert‐butylphosphanedicarbonitrile‐κP)carbonylrhodium(I), [Rh(C₅H₇O₂)(CO)(C₈H₁₃N₂)] or [Rh(acac)(CO)(^tBuP(CH₂CN)₂}] ( 2b ), (acetylacetonato‐κ²O,O′)carbonyl[3‐(diphenylphosphanyl)propanenitrile‐κP]rhodium(I), [Rh(C₅H₇O₂)(C₁₅H₁₄N)(CO)] or [Rh(acac)(CO){Ph₂P(CH₂CH₂CN)}] ( 2h ), and (acetylacetonato‐κ²O,O′)carbonyl[3‐(di‐tert‐butylphosphanyl)propanenitrile‐κP]rhodium(I), [Rh(C₅H₇O₂)(C₁₁H₂₂N)(CO)] or [Rh(acac)(CO){^tBu₂P(CH₂CH₂CN)}] ( 2i ), showed a square‐planar geometry around the Rh atom with a significant trans influence over the acetylacetonate moiety, evidenced by long Rh—O bond lengths as expected for poor π‐acceptor phosphines. The Rh—P distances displayed an inverse linear dependence with the coupling constants J_P‐Rh and the IR ν(C[triple‐bond]O) bands, which accounts for the Rh—P electronic bonding feature (poor π‐acceptors) of these complexes. A combined study from density functional theory (DFT) calculations and an evaluation of the intramolecular H…Rh contacts from X‐ray diffraction data allowed a comparison of the conformational preferences of these complexes in the solid state versus the isolated compounds in the gas phase. For 2b , 2h and 2i , an energy‐framework study evidenced that the crystal structures are mainly governed by dispersive energy. In fact, strong pairwise molecular dispersive interactions are responsible for the columnar arrangement observed in these complexes. A Hirshfeld surface analysis employing three‐dimensional molecular surface contours and two‐dimensional fingerprint plots indicated that the structures are stabilized by H…H, C…H, H…O, H…N and H…Rh intermolecular interactions.     

Synthesis,structural characterization,and thermal properties of monomeric (Mn,Co, Ni,and Zn) and polymeric (Cd) complexes of thiocyanates with benzyl carbazate as an ancillary ligand

Abstract

Five complexes [M(NCS)₂(bc)₂] M?=?Mn (1), Co (2), Ni (3), Zn (4), and [Cd(NCS)₂(bc)]_n (5), (bc) = benzyl carbazate (benzyl hydrazinecarboxylate), have been synthesized and characterized by physico-chemical and spectroscopic methods. The crystal structures of all five complexes have been confirmed by X-ray structural analysis. These results confirm that 1–4 are isotypes, and all four are centrosymmetric, with two mutually trans N,O chelating (bc) ligands in equatorial positions and a pair of trans-thiocyanate anions in the axial positions. The cadmium complex (5) is a coordination polymer. The asymmetric unit contains a square planar CdN₂OS core, in which the (bc) ligand adopts an N, O bidentate coordination mode together with N and S bound thiocyanato anions. Polymer expansion increases the coordination number to six with the N and S bound thiocyanate ligands linking two adjacent complexes. This expansion results in double layers of cadmium octahedra propagating along the c axis direction. The thermal analyses of these compounds show endothermic decomposition processes to give respective metal thiocyanates as intermediates. For the Mn, Co, Ni, and Zn compounds these intermediates decompose exothermically to form metal oxides, whereas the Cd complex forms cadmium sulfide as the end product.     

Synthesis,structural, spectroscopic,and thermal studies of some transition-metal complexes of a ligand containing the amino mercapto triazole moiety

A new series of transition-metal complexes of Schiff base ligand containing the amino mercapto triazole moiety ( HL ) was prepared. The Schiff base and its metal complexes were elucidated by different spectroscopic techniques (infrared [IR], ¹H nuclear magnetic resonance, UV–Visible, mass, and electron spin resonance [ESR]), and magnetic moment and thermal studies. Quantum chemical calculations have been carried out to study the structure of the ligand and some of its complexes. The IR spectra showed that the ligand is chelated with the metal ion in a neutral, tridentate, and bidentate manner using NOS and NO donors in complexes 1 – 6 , 10–12 , and 7 and 8 , respectively, whereas it behaves in a monobasic tridentate fashion using NOS donor sites in copper(II) nitrate complex ( 9 ). The magnetic moment and electronic spectra data revealed octahedral and square pyramidal geometries for complexes 2 , 11 , 12 , and 5 – 8 and 10 , respectively. However, the other complexes were found to have tetrahedral ( 4 ), trigonal bipyramidal ( 1 and 3 ), and square planar ( 9 ) structures. Thermal studies revealed that the chelates with different crystallized solvents undergo different types of interactions and the decomposition pathway ended with the formation of metal oxygen (MO) and metal sulfur (MS) as final products. The ESR spectrum of copper(II) complex 10 is axial in nature with hyperfine splitting with ²B_1g as a ground state. By contrast, complexes 7 and 8 undergo distortion around the Cu(II) center, affording rhombic ESR spectra. The HL ligand and some of its complexes were screened against two bacterial species. Data showed that complex 12 demonstrated a better antibacterial activity than HL ligand and other chelates.     

Spectroscopic,electrochemical, theoretical characterization and biological evaluation of a ferrocenyl-substituted unsymmetric azine ligand and its Cu(II) complex

Ferrocenyl-substituted unsymmetrical azine and its Cu(II) complex were prepared. The redox active ferrocene-based azine was obtained by condensation of 1-[(E)-hydrazono]-5-bromo-2-hydroxybenzene with ferrocene carboxaldehyde. The ferrocenyl ligand and its Cu(II) complex were characterized by IR, UV–vis, NMR, X-ray, magnetic susceptibility, molar electrical conductivity measurements, and TG techniques. The redox behaviors of the ferrocene compounds were investigated by cyclic voltammetry. Structural parameters and spectroscopic properties of the ligand and the Cu(II) complex were calculated by employing density functional theory (DFT) and time-dependent DFT and compared with available experimental data. We found slightly stronger binding ability for Cu(II) complex than the free ligand. DNA binding abilities for ferrocenyl-substituted unsymmetrical azine ligand and its Cu(II) complex are higher than some reported ferrocene compounds. We also studied DNA cleavage, superoxide and DPPH radical scavenging abilities of the compounds. Furthermore, the synthesized organometallic compounds can be bound to DNA through an intercalative mode.     

Synthesis,crystal, molecular and electronic structures of thiocyanate ruthenium(II) complexes with pyrazole,benzimidazole and triazole ligands

The [Ru(SCN)₂(PPh₃)₂(L)₂] complexes, where L = HPz, PhIm, HTz, have been prepared and studied by IR, NMR, UV–vis spectroscopy and X-ray crystallography. The complexes were prepared in the reactions of [RuCl₂(PPh₃)₃] with pyrazole, benzimidazole and triazole in methanol solutions. The electronic structures of the obtained compounds have been calculated using the TD–DFT method.     

Synthesis,structural characterization,density functional theory calculations and biological evaluation of a new organotin(IV) complex containing N‐isonicotinyl‐N',N″‐diaryl phosphorictriamide as N‐donor ligand

A new diorganotin(IV) complex with the formula SnCl₂(CH₃)₂L₂ ( C_1a ), L = 4‐NC₅H₄CONHPO(NCH₃CH₂C₆H₅)₂, was synthesized and characterized using ¹H NMR, ¹³C NMR, ³¹P NMR, ¹¹⁹Sn NMR and infrared spectroscopies. The molecular structure of C_1a was determined using X‐ray crystallography, revealing that C_1a contains hexa‐coordinated Sn(IV) centres with trans‐configuration of donor atoms around them. Each Sn(IV) atom is positioned in the centre of inversion of an octahedron. C_1a forms one‐dimensional chains via two equal intermolecular P?O…H? N hydrogen bonds. These hydrogen bonds produce centrosymmetric rings as a supramolecular hydrogen‐bonded pattern. In order to compare the relative stability of C_1a (with N‐ligated configuration) and its possible O‐ligated isomer, C_1b , density functional theory calculations were performed, the results showing a preference of C_1a over C_1b from an energy point of view. Also, natural bond orbital analysis was carried out to obtain detailed information on the electronic features of the optimized structures. The theoretical results show that intermolecular hydrogen bonding in the crystal structure has a significant role in the stabilization of C_1a , and Sn(IV) interacts more strongly with the N_py atom than the P?O functional group. Furthermore, the free ligand and its complex were tested against three human cancer cell lines, i.e. human cervical carcinoma (HeLa), human prostate cancer (PC‐3) and human breast adenocarcinoma cancer (MCF‐7). C_1a displays moderate to good cytotoxicity towards all three cancer cell lines. Moreover, antibacterial tests were carried out using the disc‐diffusion method, in which C_1a shows high activity against selected Gram‐negative and Gram‐positive bacteria. Copyright © 2015 John Wiley & Sons, Ltd.     

A new heteroleptic phosphorescent cuprous complex supported by a BINAP ligand: synthesis,structure, luminescence properties and theoretical analyses

Luminescent cuprous complexes are an important class of coordination compounds due to their relative abundance, low cost and ability to display excellent luminescence. The heteroleptic cuprous complex solvate rac‐(acetonitrile‐κN)(3‐aminopyridine‐κN)[2,2′‐bis(diphenylphosphanyl)‐1,1′‐binaphthyl‐κ²P,P′]copper(I) hexafluoridophosphate dichloromethane monosolvate, [Cu(C₅H₆N₂)(C₂H₃N)(C₄₄H₃₂P₂)]PF₆·CH₂Cl₂, conventionally abbreviated as [Cu(3‐PyNH₂)(CH₃CN)(BINAP)]PF₆·CH₂Cl₂, ( I ), where BINAP and 3‐PyNH₂ represent 2,2′‐bis(diphenylphosphanyl)‐1,1′‐binaphthyl and 3‐aminopyridine, respectively, is described. In this complex solvate, the asymmetric unit consists of a cocrystallized dichloromethane molecule, a hexafluoridophosphate anion and a complete racemic heteroleptic cuprous complex cation in which the cuprous centre, in a tetrahedral CuP₂N₂ coordination, is coordinated by two P atoms from the BINAP ligand, one N atom from the 3‐PyNH₂ ligand and another N atom from a coordinated acetonitrile molecule. The UV–Vis absorption and photoluminescence properties of this heteroleptic cuprous complex have been studied on polycrystalline powder samples, which had been verified by powder X‐ray diffraction before recording the spectra. Time‐dependent density functional theory (TD‐DFT) calculations and a wavefunction analysis reveal that the orange–yellow phosphorescence emission should originate from intra‐ligand (BINAP) charge transfer mixed with a little of the metal‐to‐ligand charge transfer ³(IL+ML)CT excited state.     

Synthetic and structural studies of the diiron toluenedithiolate carbonyl complexes with monophosphine ligands

Four diiron toluenedithiolate complexes 2–5 with monophosphine ligands are reported. Treatment of [μ-SC₆H₃(CH₃)S-μ]Fe₂(CO)₆ (1) with tris(3-chlorophenyl)phosphine, tris(4-chlorophenyl)phosphine, tris(4-methylphenyl)phosphine or 2-(diphenylphosphino)benzaldehyde, and Me₃NO?2H₂O in MeCN resulted in the formation of [μ-SC₆H₃(CH₃)S-μ]Fe₂(CO)₅[P(3-C₆H₄Cl)₃] (2), [μ-SC₆H₃(CH₃)S-μ]Fe₂(CO)₅[P(4-C₆H₄Cl)₃] (3), [μ-SC₆H₃(CH₃)S-μ]Fe₂(CO)₅[P(4-C₆H₄CH₃)₃] (4), and [μ-SC₆H₃(CH₃)S-μ]Fe₂(CO)₅[Ph₂P(2-C₆H₄CHO)] (5) in 64–82% yields. Complexes 2–5 have been characterized by elemental analysis, IR, ¹H NMR, ³¹P{¹H} NMR, ¹³C{¹H} NMR and further confirmed by single crystal X-ray diffraction analysis. The molecular structures show that 2–5 contain a butterfly diiron toluenedithiolate cluster coordinated by five terminal carbonyls and an apical monophosphine.     

Synthesis,characterization, and biological screening of metal complexes of novel sulfonamide derivatives: Experimental and theoretical analysis of sulfonamide crystal

This study reports the synthesis of sulfonamide-derived Schiff bases as ligands L ¹ and L ² as well as their transition metal complexes [VO(IV), Fe(II), Co(II), Ni(II), Cu(II), and Zn(II)]. The Schiff bases (4-{E-[(2-hydroxy-3-methoxyphenyl)methylidene]amino}benzene-1-sulfonamide ( L ¹ ) and 4-{[(2-hydroxy-3-methoxyphenyl)methylidene]amino}-N-(5-methyl-1,2-oxazol-3-yl)benzene-1-sulfonamide ( L ² ) were synthesized by the condensation reaction of 4-aminobenzene-1-sulfonamide and 4-amino-N-(3-methyl-2,3-dihydro-1,2-oxazol-5-yl)benzene-1-sulfonamide with 2-hydroxy-3-methoxybenzaldehyde in an equimolar ratio. Sulfonamide core ligands behaved as bidentate ligands and coordinated with transition metals via nitrogen of azomethine and the oxygen of the hydroxyl group. Ligand L ¹ was recovered in its crystalline form and was analyzed by single-crystal X-ray diffraction technique which held monoclinic crystal system with space group (P2₁/c). The structures of the ligands L ¹ and L ² and their transition metal complexes were established by their physical (melting point, color, yields, solubility, magnetic susceptibility, and conductance measurements), spectral (UV–visible [UV–Vis], Fourier transform infrared spectroscopy, ¹H NMR, ¹³C NMR, and mass analysis), and analytical (CHN analysis) techniques. Furthermore, computational analysis (vibrational bands, frontier molecular orbitals (FMOs), and natural bonding orbitals [NBOs]) were performed for ligands through density functional theory utilizing B3LYP/6-311+G(d,p) level and UV–Vis analysis was carried out by time-dependent density functional theory. Theoretical spectroscopic data were in line with the experimental spectroscopic data. NBO analysis confirmed the extraordinary stability of the ligands in their conjugative interactions. Global reactivity parameters computed from the FMO energies indicated the ligands were bioactive by nature. These procedures ensured the charge transfer phenomenon for the ligands and reasonable relevance was established with experimental results. The synthesized compounds were screened for antimicrobial activities against bacterial (Streptococcus aureus, Bacillus subtilis, Eshcheria coli, and Klebsiella pneomoniae) species and fungal (Aspergillus niger and Aspergillus flavous) strains. A further assay was designed for screening of their antioxidant activities (2,2-diphenyl-1-picrylhydrazine radical scavenging activity, total phenolic contents, and total iron reducing power) and enzyme inhibition properties (amylase, protease, acetylcholinesterase, and butyrylcholinesterase). The substantial results of these activities proved the ligands and their transition metal complexes to be bioactive in their nature.     

Synthesis and solid-state structural characterisation of Pt(II,IV) bromide complexes containing bidentate organothiomethylpyridine heteroleptic ligands

A convenient synthetic method for the preparation of organothiomethylpyridine ligands 2-(RSCH₂)C₅H₄N (R = Ph (L¹), Me (L²)), 2-MeS–6-Me-C₅H₃N (L³), and 2-MeS–4-Me-C₅H₃N (L⁴) via the initial lithiation of substituted 2-picolines followed by the nucleophilic reaction with a diorganyldisulfide is described. The complexes [PtBr₂L] (L = L¹–L⁴) have been prepared in good to high yields as yellow solids with low solubility in organic solvents. The solid state structures of the complexes have been determined, showing the spatial arrangement of the complexes to depend significantly upon varying substituents within the ligand. The complexes undergo oxidation by bromine to form the tetravalent complexes [PtBr₄(L)] (L = L¹–L⁴). The solid state structures of [PtBr₄(L²)] and [PtBr₄(L₄)] have been determined, and shown to be monomeric with the ligand chelating the platinum centre.     

Synthesis and structural characterization of Ni(II) complexes containing a heterocyclic NO donor ligand

Five novel nickel(II) complexes have been successfully synthesized with a heterocyclic ligand, Opdac, [Ni(Opdac)₂]Cl₂ (1), [Ni(Opdac)₂(CH₃OH)₂]Br₂(CH₃OH)₂ (2), [Ni(Opdac)₂]I₂ (3), [Ni(Opdac)₂NO₃]NO₃ (4) and [Ni(Opdac)₂ClO₄]ClO₄ (5) where Opdac = 4-(1-H-1,3-benzimidazole-2-yl)-1,5-dimethyl-2-phenyl-1-2-dihydro-3-H-pyrazol-3-one. All the complexes were characterized by elemental analysis, molar conductivity, CHN analysis, magnetic susceptibility measurements, spectroscopic studies and TG/DTA methods. In all the complexes, Opdac acts as a bidentate ligand coordinating to Ni(II) ion via the benzimidazole imine nitrogen and the pyrazolone oxygen atoms. The complexes 1 and 3 have a tetrahedral geometry while 2, 4 and 5 have an octahedral geometry around the Ni(II) center.     

Synthesis and characterization of some binuclear metal complexes with a pentadentate azodye ligand: An experimental and theoretical study

A novel series of binuclear complexes with Mn(II), Co(II), Ni(II), Cu(II), Zn(II), and Cd(II) ions derived from a pentadentate azo dye ligand (H₃L) was synthesized and structurally investigated by various physicochemical analyses, namely, scanning electron microscopy, transmission electron microscopy, NMR, UV–visible spectroscopy, and Electron-Spin Resonance (ESR) studies. The infrared spectral data revealed characteristic bands due to ν(N=N) and ν(C=O) at 1606 and 1631 cm⁻¹ in the free ligand. However, their positions shifted and appeared at ~1564 and ~1592 cm⁻¹ on coordination, suggesting the involvement of carbonyl oxygen and azo nitrogen in complex formation. The spectral data suggested octahedral geometry for the complexes. The kinetic parameters such as order and activation energy were determined from the thermal decomposition values. X-ray powder diffraction analysis showed the orthorhombic nature of the cadmium complex. Furthermore, Density functional theory (DFT) calculations were also recorded to describe the insight bonding. The synthesized compounds were tested for in vitro antibacterial activity against K. aerogenes, S. aureus, B. acidoterrestris, E. coli, and V. cholerae strains by the cup-plate method. In addition, the interactions that occurred in the protein–ligand complexes have been predicted by docking analysis.