Synthesis, Spectroscopic and Electrochemical Investigations of Two vic-Dioximes and Their Mononuclear Ni（Ⅱ）, Cu（Ⅱ） and Co（Ⅱ） Metal Complexes Containing Morpholine Group

Two vic-dioxime ligands （LxH2） containing morpholine group have been synthesized from 4-[2-（dimethylaminoethyl）] morpholine with anti-phenylchloroglyoxime or anti-monochloroglyoxime in absolute THF at -15 ℃. Reaction of two vic-dioxime ligands with MCl2·nH2O （M： Ni, Cu or Co and n=2 or 6） salts in 1 ： 2 molar ratio afforded metal complexes of type [M（LxH）2] or [M（LxH）2·2H2O]. All of metal complexes are non-electrolytes as shown by their molar conductivities （Am） in DMF （dimethyl formamide） at 10^-3 mol·L^-1. Structures of the ligands and metal complexes have been solved by elemental analyses, FT-IR, UV-Vis, ^1H NMR and ^13C NMR, magnetic susceptibility measurements, molar conductivity measurements. Furthermore, redox properties of the metal complexes were investigated by cyclic voltammetry.     

Synthesis,Structural, and Antibacterial Studies of Some Mixed Ligand Complexes of Zn(II), Cd(II), and Hg(II) Derived From Citral Thiosemicarbazone and N-Phthaloyl Amino Acids

A series of new mixed ligand complexes of Zn(II), Cd(II), and Hg(II) with cis-3,7-dimethyl-2,6-octadienthiosemicarbazone (CDOTSC; LH) and N-phthaloyl amino acids (AH) have been synthesized by the reaction of metal dichloride with ligands CDOTSC and N-phthaloyl derivative of DL-glycine (A₁H), L-alanine (A₂H), or L-valine (A₃H) in a 1:1:1 molar ratio in dry refluxing ethanol. All the isolated complexes have the general composition [M(L)(A)]. The plausible structure of these newly synthesized complexes has been proposed on the basis of elemental analyses, molar conductances, molecular weight measurement, and various spectral (IR, ¹H NMR, and ¹³C NMR) studies, and four coordinated geometries have been assigned to these complexes. All the complexes and ligands have been screened for their antibacterial activity.     

Spectral characterization and biocidal activity of organotin(IV) (E)-3-[(2′,6′-dichlorophenylamido)]propenoates

Biocidal and spectroscopic aspects of organotin(IV) complexes with (E)-3-[(2′,6′-dichlorophenylamido)]propenoic acid are described with support of elemental analysis. IR, ¹H, ¹³C, ¹¹⁹Sn NMR and mass spectral data suggest that the ligand is bidentate, coordinating through oxygen atoms and that diorganotin(IV) complexes are six-coordinate. Triorganotin(IV) carboxylates exist as pentacoordinated trigonal bipyramidal complexes in the solid state and tetrahedral ones in solution. The complexes have been screened against bacteria, fungi and brine-shrimp larvae to assess their biological activity.     

Synthesis,Spectroscopic Characterization,and Antifungal Activity of Some Mixed Ligand Complexes of Zn(II), Cd(II), and Hg(II)

A series of new mixed ligand complexes of Zn(II), Cd(II), and Hg(II) with citronellal thiosemicarbazone [3,7-dimethyl-6-octene-1-a1 thiosemicarbazone (LH)] and N-phthaloyl amino acids (AH) have been synthesized by the reaction of metal(II) chloride with ligands citronellal thiosemicarbazone (DOTSC) and N-phthaloyl glycine [1,3-dihydro-1,3-dioxo-2H-isoindole-2-acetic acid (A₁H)] or N-phthaloyl alanine [1,3-dihydro-1,3-dioxo-α(methyl)-2H-isoindole-2-acetic acid (A₂H)] in 1:1:1 molar ratio in dry refluxing ethanol. All the complexes have been characterized by elemental analyses, molar conductance measurement, molecular weight measurement, IR, and multinuclear NMR (¹H and ¹³C{¹H}) spectral studies. IR, ¹H, and ¹³C{¹H} NMR spectral studies suggest the involvement of azomethine-N, thiol-S atoms of the thiosemicarbazone moiety and both carboxylate-O of N-phthaloyl amino acid moiety in coordination with central metal(II) ion, and four coordinated geometries have been assigned to these complexes. The free ligands and metal complexes have been screened for their antifungal activity against two fungal strains, Fusarium moniliformae and Macrophomina phaseolina, using the the radial growth method. The results of antifungal activity show that metal complexes show enhanced higher activity than the free ligands.

Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file.     

Synthetic, structural and biological studies of organotin(IV) complexes of schiff bases derived from pyrrol-2-carboxaldehyde

Some new organotin(IV) complexes having general formulae R₂MCl[L] and R₂M[L]₂ were synthesized by the reactions of Me₂MCl₂ with Schiff bases [5-Mercapto-4-(pyrrolcarboxalideneamino)-s-triazole, 5-Mercapto-3-methyl-4-(2-pyrrolcarboxalideneamino)- s-triazole, 3-Ethyl-5-mercapto-4-(2-pyrrolcarboxalideneamino)-s-triazole] in 1:1 and 1:2 molar ratios. All of the compounds were characterized by elemental analysis, molar conductance, IR, UV, ¹H, ¹³C and ¹¹⁹Sn NMR spectral studies. The IR and ¹H NMR spectral data suggest the involvement of azomethine nitrogen in coordination with the central metal atom. With the help of the above-mentioned spectral studies, penta and hexacoordinated environments around the central metal atoms in the 1:1 and 1:2 complexes, respectively, have been proposed. Finally, the free ligands and their metal complexes were tested in vitro against some pathogenic bacteria and fungi to assess their antimicrobial properties.     

Preparation,spectroscopic investigation and antibacterial activity of some organomercury(II) and organotin(IV) dithio complexes

Phenylmercuric acetate, triphenyltin chloride and dibutyltin chloride react with alkali‐metal or ammonium salts of some 1,1‐ and 1,2‐dithio ligands in appropriate molar ratios to yield a series of organometallic dithio complexes of the type [PhHgX] (X = butylxanthate (Buxant⁻), cyclohexylxanthate (Cyxant⁻), benzylxanthate (Bzxant⁻) or pyrrolidin‐1‐yldithiocarbamate (Pdtc⁻); [(PhHg)₂X] (X = isomaleonitriledithiolate (i‐MNT²⁻) or 1‐ethoxycarbonyl‐1‐cyanoethylene‐2,2‐dithiolate (ecda²⁻); Ph₃SnX (X = Buxant⁻ or Pdtc⁻); [(Ph₃Sn)₂(i‐MNT)] and [Bu₂SnMNT] (MNT²⁻ = maleonitriledithiolate). These complexes have been characterized by elemental analysis, molar conductance measurements, IR, FT‐Raman, ¹H and ¹³C NMR and fast atom bombardment (FAB) mass spectra. Cyclic dimeric structures for phenylmercuryxanthates and monomeric structures for the remaining complexes are suggested. Antibacterial activities of the complexes and parent ligands have been screened against some well‐known pathogenic bacteria. Organomercury dithiolates have been found to be more potential antibacterial than organotin complexes. Copyright © 2000 John Wiley & Sons, Ltd.     

Complexes of Co(II), Ni(II), Cu(II), and Pd(II) with Sulfametrole-Cyclodiphosph(V)azane Derivatives

Novel [1,3-di-[N ₁ -4-methoxy-1,2,5-thiadiazole-3-yl-sulfanilamide(sulfametrole)]-2″4-bis-[1,3-dithiole-2-thione-4,5-dithiolate]-2′,4′-dichl-orocyclodiphosph(V)azane] (III) , was prepared and their coordinating behavior towards the metal ions Co(II), Ni(II), Cu(II), and Pd(II) was studied. The structures of the isolated products are proposed based on elemental analyses, IR, UV, ¹ H, and ³¹ P NMR, ESR, magnetic susceptibility, molar ratio, conductometric titration and electrical conductivity measurements. The prepared complexes showed high to moderate bactericidal activity compared with the ligand.     

Design,synthesis, DNA binding ability,chemical nuclease activity and antimicrobial evaluation of Cu(II), Co(II), Ni(II) and Zn(II) metal complexes containing tridentate Schiff base

A novel Schiff base has been designed and synthesized using the bioactive ligand obtained from 4-aminoantipyrine, 3,4-dimethoxybenzaldehyde and 2-aminobenzoic acid. Its Cu(II), Co(II), Ni(II), Zn(II) complexes have also been synthesized in ethanol medium. The structural features have arrived from their elemental analyses, magnetic susceptibility, molar conductance, mass, IR, UV–Vis, ¹H NMR and ESR spectral studies. The data show that the complexes have composition of ML₂ type. The electronic absorption spectral data of the complexes suggest an octahedral geometry around the central metal ion. The interaction of the complexes with calf thymus (CT) DNA has been studied using absorption spectra, cyclic voltammetric, and viscosity measurement. The metal complexes have been found to promote cleavage of pUC19 DNA from the super coiled form I to the open circular form II. The complexes show enhanced antifungal and antibacterial activities compared with the free ligand.     

Chloro-diorganotin(IV) complexes of 4-methyl-1-piperidine carbodithioic acid: Synthesis, X-ray crystal structures, spectral properties and antimicrobial studies

Chloro-diorganotin(IV) complexes of 4-methyl-1-piperidine carbodithioic acid (4-MePCDTA) have been synthesized by the reaction with diorganotin dichloride in 1:1 molar ratio in anhydrous toluene. These newly synthesized complexes have been characterized by elemental, IR, multinuclear NMR (¹H and ¹³C) and mass spectrometric studies. The crystal structures of complex 1 [Me₂SnCl(4-MePCDT)] and 3 [Ph₂SnCl(4-MePCDT)] have been determined by X-ray single crystal analysis, which show trigonal bipyramid geometry. These complexes were tested for their antimicrobial activity against six different plant and human pathogens. The screening results show that the complexes exhibit higher antibacterial and antifungal activity than the free ligand.     

Synthesis, characterization, and biological activities of some transition metal(II) complexes with the thiosemicarbazone derived from 4-[1-(4-methylphenylsulfonyl)-1H-indol-3-yl]but-3-en-2-one

A new 4-[1-(4-methylphenylsulfonyl)-1H-indol-3-yl]but-3-en-2-one thiosemicarbazone (HL) was synthesized derived from 4-[1-(4-methylphenylsulfonyl)-1H-indol-3-yl]but-3-en-2-one. Four transition metal(II) complexes of HL have been prepared. Elemental analysis, molar conductivity, IR, UV, ¹H NMR spectra, and TG-DTA have been used to characterize these complexes. The complexes have the general formula ML₂, where M = Zn, Cu, Co, and Ni. The ligand and its complexes have been studied for their possible biological activity including anti-inflammatory, antibacterial, and antitumour activity in vitro.     

Antitumor Activity and Physicochemical Properties of New Thiosemicarbazide Derivative and Its Co(II), Ni(II), Cu(II), Zn(II) and Cd(II) Complexes

A novel biologically active thiosemicarbazide derivative ligand L (N-[(phenylcarbamothioyl)amino]pyridine-3-carboxamide) and a series of its five metal(II) complexes, namely: [Co(L)Cl₂], [Ni(L)Cl₂(H₂O)], [Cu(L)Cl₂(H₂O)], [Zn(L)Cl₂] and [Cd(L)Cl₂(H₂O)] have been synthesized and thoroughly investigated. The physicochemical characterization of the newly obtained compounds has been performed using appropriate analytical techniques, such as ¹H and ^l3C nuclear magnetic resonance (NMR), inductively coupled plasma (ICP), thermogravimetric analysis (TGA), Fourier-transform infrared spectroscopy (FTIR) and magnetic measurements. In order to study the pharmacokinetic profile of the compounds, ADMET analysis was performed. The in vitro studies revealed that the synthesized compounds exhibit potent biological activity against A549 human cancer cell line.     

Synthesis and Structural Characterization of Cadmium(II) and Mercury(II) Complexes Derived from 3‐Aminoquinoline

Two novel metal complexes derived from interactions of Cd²⁺ and Hg²⁺ ions with 3‐aminoquinoline in the molar ratio 1 : 2 are reported. The synthesized and isolated metal complexes were characterized by UV/VIS, FT‐IR, ¹H‐ and ¹³C‐NMR, and ESI‐MS spectroscopic studies, and elemental analyses. FT‐IR and NMR studies confirmed that the NH₂ group remains uncoordinated in both synthesized complexes. The molecular structure of the Cd^II complex was additionally determined by X‐ray single‐crystal analysis. The Cd complex crystallizes in the triclinic centrosymmetric P$\bar 1$ space group. Moreover, the Cd^II complex exists as neutral discrete molecule and was found to show tetrahedral geometry.     

Dinuclear peroxo complexes of molybdenum(VI) containing Mannich base ligands

Dinuclear molybdenum(VI) peroxo complexes containing Mannich base ligands having formulae [Mo₂O₄(O₂)₂L-L(H₂O)₂] · H₂O [where L-L = N-[1-morpholinobenzyl] acetamide (MBA), N-[1-piperidinobenzyl] acetamide (PBA), N-[1-morpholino(-4-nitrobenzyl)] benzamide (MPNBB), N-[1-piperidino(-3-nitrobenzyl)] benzamide (PMNBB), N-[1-morpholino(-2-nitrobenzyl)] acetamide (MONBA), and N-[1-morpholino(-3-nitrobenzyl)] acetamide (MMNBA)] have been synthesized by stirring ammonium heptamolybdate with excess 30% aqueous hydrogen peroxide followed by treatment with ethanolic solution of corresponding ligands. The complexes have been characterized by elemental analysis, molar conductance, magnetic measurements, infrared (IR), electronic, TGA/DTA, mass spectral, and ¹H NMR studies. The complexes are non-electrolytes and diamagnetic. The IR spectral studies suggest that the ligands are bidentate to metal through carbonyl oxygen and ring nitrogen. Thermal analyses provide conclusive evidence for the presence of coordinated, as well as lattice water in the complexes. Dinuclear complexes preserve the individuality of the molybdenum oxo peroxo core. The complexes exhibit higher antibacterial activity against bacterium Ralastonia solanacearum (Pseudomonas solanacearum) than the free ligands.     

Synthesis,characterization and biological properties of Co(II), Ni(II), Cu(II) and Zn(II) complexes with an SNO functionalized ligand

Some new metal(II) complexes, ML₂[M = Co, Ni, Cu and Zn], of 2-acetylthiophene benzoylhydrazone ligand (HL) containing a trifunctional SNO-donor system have been synthesized and characterized on the basis of physicochemical data by elemental analysis, magnetic moment, molar conductance, thermogravimetric and spectroscopic (electronic, IR, ¹H NMR and ¹³C NMR) data. The ligand functions as monobasic SNO tridentates where the deprotonated enolic form is preferred in the coordination producing distorted octahedral complexes.     

Synthesis,characterization and antibacterial activity of some new complexes of Cu(II), Ni(II), VO(II), Mn(II) with Schiff base derived from 4-amino-2,3-dimethyl-1-phenyl-3-pyrazolin-5-one

Coordination compounds of Cu(II), VO(II), Ni(II), and Mn(II) with the Schiff base obtained through the condensation of 4-amino-2,3-dimethyl-1-phenyl-3-pyrazolin-5-one with 3-formyl-6-methyl-chromone were synthesized. The characterization of the newly formed compounds was done by ¹H NMR, UV–Vis, IR, ESR spectroscopy, elemental analysis and molar electric conductibility. The crystal structure of 1-phenyl-2,3-dimethyl-4-(N-3-formyl-6-methyl-chromone)-3-pyrazolin-5-one (HL) has been determined by X-ray diffraction studies, as well as the one of its copper(II) complex [CuL(OAc)]·CH₃OH which contains an anionic ligand and an acetate in the coordination sphere of the metal. The single crystal X-ray structure for (HL) was analyzed for its various weak H-bonding and dimeric association.     

Synthesis and characterization of bis(diphenylphosphinomethyl)amino ligands and their Ni(II), Pd(II) complexes: Application to hydrogenation of styrene

Transition metal complexes of Ni(II) and Pd(II) with ditertiary bis(diphenylphosphinomethyl)amino ligands, (Ph₂PCH₂)₂NC(CH₃)₃ ( 1 ) and [(Ph₂PCH₂)Nm‐PhSO₃]Na ( 2 ) (Ph = phenyl), have been synthesized in good yields under nitrogen atmosphere by Schlenk technique. All complexes have been characterized using elemental analyses and spectroscopic techniques such as atomic absorption, FT‐IR, and NMR (¹H, ³¹P). Atomic absorption spectroscopic analysis showed that the reactions of ligands 1 and 2 with NiCl₂ ⋅ 6H₂O and [PdCl₂(COD)] occurred in 1:1 molar ratio. The metal complexes [NiCl₂(Ph₂PCH₂)₂Nm‐PhSO₃Na] ( 4 ) and [PdCl₂(Ph₂PCH₂)₂Nm‐PhSO₃Na] ( 6 ) were found to be soluble in ethanolic and aqueous solutions, as well as slightly soluble in water. Electrochemical behaviors of complexes were investigated by cyclic voltammetry. Catalytic effects of Pd(II) complexes were tested throughout the hydrogenation of styrene to ethylbenzene. © 2008 Wiley Periodicals, Inc. Heteroatom Chem 19:113–118, 2008; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20384     

The synthesis and characterization of three new vic -dioximes and their nickel(II), copper(II) and cobalt(II) complexes

Three new vic-dioximes, [L¹H₂], N-(4-ethylphenyl)amino-1-acetyl-1-cyclohexenylglyoxime, [L²H₂], N-(4-butylphenyl)amino-1-acetyl-1-cyclohexenylglyoxime, and [L³H₂], N-(4-methoxyphenyl)amino-1-acetyl-1-cyclohexenylglyoxime were synthesized from 1-acetyl-1-cyclohexeneglyoxime and the corresponding substituted aromatic amines. Metal complexes of these ligands were also synthesized with Ni(II), Cu(II), and Co(II) salts. These new compounds (ligands and complexes) were characterized with FT–IR, magnetic susceptibility measurement, molar conductivity measurements, mass spectrometry measurements, thermal methods (e.g. thermal gravimetric analysis), ¹H NMR (Nuclear Magnetic Resonance) and ¹³C NMR spectral data and elemental analyses.     

Synthesis,characterization and crystal structures of cyclometallated Ru(II) carbonyl complexes formed by hydrazones

Cyclometallated Ru(II) complexes of the type [Ru(CO)(EPh₃)₂(L)] (E = P or As; L = tridentate hydrazone-derived ligand) have been obtained by refluxing an ethanolic solution of [RuHCl(CO)(PPh₃)₃] or [RuHCl(CO)(AsPh₃)₃] with the hydrazone derivatives H₂php (2-[(2,4-dinitro-phenyl)-hydrazonomethyl]-phenol), H₂phm (2-[(2,4-dinitro-phenyl)-hydrazonomethyl]-6-methoxy-phenol) and H₂phn (2-[(2,4-dinitro-phenyl)-hydrazonomethyl]-naphthalen-1-ol). The formation of stable cyclometallated complexes has been authenticated by single crystal X-ray structure determination of two of the complexes, and the mechanism of C–H activation is discussed in detail. The spectral (IR, UV–Vis and ¹H NMR) and electrochemical data for all the complexes are reported. Electrochemistry shows a substantial variation in the metal redox potentials with regard to the electronic nature of the substituents present in the hydrazone derivative.     

Synthesis,characterization, DNA interaction,thermal and in vitro biological activity investigation of some Ni(II)-Isatin bishydrazone complexes

Complexes of the type [Ni (L) (H₂O)] Cl₂.nH₂O, where L = [(pyridine-2-carboxaldhyde)-3-isatin]-bishydrazone (cpish), [(2-acetyl pyridine)-3-isatin]-bishydrazone (apish) and [(2-benzoyl pyridine)-3-isatin]-bishydrazone (bpish) have been synthesized and characterized on the bases of elemental analysis, molar conductance, IR, NMR, electronic spectra and thermal analysis (TGA and DTA). Moreover, the stoichiometry and the formation constants of these complexes have been determined spectrophotometrically. Kinetics and thermodynamic parameters of the thermal decomposition have been computed from the thermal data using Coats and Redfern method, which confirm first-order kinetics. The bioefficacy of the ligands and their complexes have been examined for their in vitro antibacterial and antifungal activity against many types of bacteria and anti fungal cultures, which are common contaminants of the environment in Egypt, and the results indicate that the ligands and their metal complexes possess notable antimicrobial activity. Investigation of their interaction with CT-DNA under physiological conditions, using spectroscopic (UV–visible) and hydrodynamic techniques (viscosity measurements). Binding constant "K _b" obtained from spectroscopic methods revealed significant binding of compounds with DNA via intercalation, Furthermore, free energies of compounds–DNA interactions indicated spontaneity of their binding.     

Mixed ligand complexes of tungsten(VI) containing aroyl hydrazones and isothiocyanate

Five complexes [WO(NCS)₄L–L] (where L–L = benzoic acid[1-(Furan-2-yl)methylene]hydrazide(BFMH), benzoic acid[(thiophen-2-yl)methylene]hydrazide(BTMH), benzoic acid[1-(thiophen-2-yl)ethylidene]hydrazide(BTEH), benzoic acid(phenylmethylene)hydrazide(BPMH) and benzoic acid[1-(anisol-3-yl) methylene]hydrazide(BAMH)) have been prepared by reaction of ammonium tetraisothiocyanatodioxotungstate(VI) with the corresponding ligand in aqueous medium in the presence of hydrochloric acid. The complexes have been characterized by elemental analysis, molar conductivity, magnetic moment measurements, IR, electronic spectra, thermogravimetric analysis TGA/DTA and ¹H NMR.