Preparation,characterization, and catalytic activity of polymer supported ethylenediamine and glycine cobalt complexes

Polymer-supported ethylenediamine cobalt chloride and glycine cobalt chloride have been prepared with 2, 5, and 10% divinylbenzene (DVB) styrene copolymer macroporous beads by sequential attachment of the bifunctional ligand followed by treatment of metal salt with the functionalized polymer beads. Physicochemical properties like moisture content, bulk density, swelling, and thermal stability of the supported catalysts have been studied. Probable structures have been proposed based on spectroscopic data obtained from electronic, infrared, far-infrared, and in some cases ESCA. Catalytic activity have been tested for hydrogenation of 1-octene and decomposition of hydrogen peroxide as model reactions.     

钴(Ⅱ)、镍(Ⅱ)、铜(Ⅱ)与2,4-二羟基二苯甲酮配合物的合成与表征

以2,4-二羟基二苯甲酮(BP)为配体与M2+(M=Co,Ni,Cu)合成了几种新的配合物,研究了配合物的热稳定性。通过元素分析、IR、UV、TG-DTA和电导分析对配合物进行了表征。结果表明配合物的组成为M(BP)2.nH2O,配体中羰基氧和邻位羟基氧与中心离子配位构成平面正方形结构,三种配合物的热稳定性为:Co(Ⅱ)>Ni(Ⅱ)>Cu(Ⅱ)。     

Synthesis and Characterization of Poly[thiadiazoledithiocarbamate] and Some Metal Complexes

Poly[thiadiazoledithiocarbamate] (PTDTC) is prepared from the reaction of 2-amino-5-mercapto-1,3,4-thiadiazole with carbon disulfide followed by in situ removal of hydrogen sulfide gas. Three polymer-metal complexes of cobalt, copper and lead are prepared from the reaction of PTDTC with the metal salts in DMSO. The polymer-metal complexes are investigated by elemental analysis, electronic spectra, Fourier Transform infrared spectroscopy and magnetic susceptibility. The DC electrical conductivity variation with temperature in the range 300–500 K of the annealed polymer, the 5% I₂ doped polymer and the polymer-copper complex is determined for comparison. All the polymer-metal complexes are high melting, thermally stable materials that are insoluble in most common organic solvents.     

Polymers containing metal chelate units. I. Immobilized mono- and binuclear chelates of nickel(II) and cobalt(II)

A number of polymer carriers with chelating groups such as diketones, diacylamines, and enaminoketones has been synthesized. The immobilized mono- and binuclear chelates have been prepared by the interaction of these polymeric ligands with nickel(II) and cobalt(II) acetates in alcohol. Spectral and magnetic data confirm the tetrahedral structure of the cobalt complexes and octahedral structure of the nickel complexes. The catalytic properties of the immobilized complexes in ethylene dimerization and butadiene polymerization have been investigated.     

二环己酮草酰二腙桥联的双核钴(Ⅱ)配合物的合成、表征及电化学行为

合成了二种含二环己酮草酰二腙桥的双核钴配合物 [Co2 ( BCO) ( Mephen) 4]( Cl O4 ) 4( 1 )和[Co2 ( BCO) ( Me2 phen) 4]( Cl O4 ) 4( 2 )。BCO=二环己酮草酰二腙 ,Mephen=5-甲基 - 1 ,1 0 -邻菲咯啉 ,Me2 phen=2 ,9-二甲基 - 1 ,1 0 -邻菲咯啉。使用元素分析、摩尔电导以及红外光谱和电子光谱手段对配合物进行了表征 ,推定了配合物的组成和结构。并用循环伏安法研究了配合物 [Co2 ( BCO)( Mephen) 4]( Cl O4 ) 4的电化学行为     

Spectral,thermal stability and antibacterial studies of copper,nickel and cobalt complexes of N-methyl-N-phenyl dithiocarbamate

Copper(II), cobalt(II) and nickel(II) bis(N-methyl-N-phenyl dithiocarbamate) complexes having the general formula [M{S₂CN(MePh)}₂] (where M?=?Cu, Co and Ni) have been prepared and characterized by spectral and thermal analysis. The IR spectra suggest that coordination of dithiocarbamate (DTC) occurred through the two sulfur atoms in a symmetrical bidentate fashion. The electronic spectra, conductance measurement and magnetic moment analysis support the proposed geometry for the electronically dilute complexes. The results of the thermal analysis showed that after dehydration, a one-step decomposition pattern leading to the formation of respective metal sulfide as the end-product occurred. The results are consistent with the proposed composition of the complexes. The in vitro antibacterial activity of the complexes was investigated against strains of gram-negative Escherichia coli, Klebsiella oxytoea and Pseudomonas aureginosa, and gram-positive Bacillus cereus, Staphylococcus aureus and Protues mirabilis. The antibacterial activity of the complexes compared favorably with that of streptomycin and augmentine against S. aureus and B. cereus. The cobalt complex had the best antibacterial activity against the test compounds with inhibitory zone range of 11–14.5?mm.     

Synthesis, Spectral Characterization and Biocidal Activity of Thermally Stable Polymeric Schiff Base and Its Polymer Metal Complexes

The polymer metal complexes of transition metal ions Mn(II), Co(II), Ni(II), Cu(II) and Zn(II) with a new polymeric Schiff base containing formaldehyde and piperazine moieties have been synthesized by the condensation and characterized by elemental analyses, infrared spectra, electronic spectra, magnetic susceptibility measurements and thermogravimetric analyses (TGA). The results of the electronic spectra and magnetic moments indicate that the polymer–metal complexes of Mn(II), Co(II) and Ni(II) have octahedral geometry, while the complexes of Cu(II) and Zn(II) show square planar and tetrahedral geometry, respectively. The analyses of the thermal curves of all the polymer metal complexes show better thermal stability than the polymeric Schiff base. All compounds show excellent antibacterial as well as antifungal activity against three types of bacteria and two types of fungi. The antimicrobial activities were determined by using the agar well diffusion method with 100 μg/mL concentrations of polymer metal complex.     

Novel ligation of some rare earth metal supramolecular polymer complexes

Summary Novel seven, nine and ten-coordinated rare earth polymer complexes of N-Acryloyl-1-phenyl-2-thiourea (APT) of the composition [Ln(NO₃)₃(APT)₂]_n (Ln = La, Sm, Tb, Pr and Nd) and [Ln(NCS)₃(APT)_x]_n (where Ln = La or Pr at x = 2 and Ln = Nd, Sm and Tb at x = 3 ) have been prepared and characterized on the basis of their chemical analyses, magnetic measurements, conductance, visible and IR spectral data. The electronic spectra of Pr³⁺, Nd³⁺ and Sm³⁺ show characteristic f-f transitions and the nephelauxetic effect (1-B) of these transitions has been evaluated. These data indicate the weak involvement of the 4f orbitals in complex formation. Composition and IR spectral data of the obtained polymeric complexes show that APT acts as a bidentate ligand. The structure and bonding of these high coordination number compounds were established and identified with the help of various physico-chemical studies. Conductance studies indicate a non-electrolytic behavior for these complexes. Their infrared spectra show that both the ligand and the nitrate group are bound to the metal ion in a bidentate fashion.     

Studies of poly(8‐hydroxy‐4‐azoquinolinephenol‐formaldehyde) and its metal complexes

Poly(8‐hydroxy‐4‐azoquinolinephenol‐formaldehyde) resin (8H4AQPF) was prepared by condensing 8‐hydroxy 4‐azoquinoline phenol with formaldehyde (1 : 1 mol ratio) in the presence of oxalic acid. Polychelates were obtained when the DMF solution of poly(8H4AQPF) containing a few drops of ammonia was treated with the aqueous solution of Cu(II) and Ni(II) ions. The polymeric resin and polymer–metal complexes were characterized with elemental analysis and spectral studies. The elemental analysis of the polymer–metal complexes suggested that the metal‐to‐ligand ratio was 1 : 2. The IR spectral data of the polychelates indicated that the metals were coordinated through the nitrogen and oxygen of the phenolic ? OH group. Diffuse reflectance spectra, electron paramagnetic resonance, and magnetic moment studies revealed that the polymer–metal complexes of the Cu(II) complexes were square planar and those of the Ni(II) complexes were octahedral. X‐ray diffraction studies revealed that the polymer metal complexes were crystalline. The thermal properties of the polymer and polymer–metal complexes were also examined. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1506–1510, 2006     

Synthesis, Spectral and Antibacterial Studies of Copper(II) Tetraaza Macrocyclic Complexes

A novel family of tetraaza macrocyclic Cu(II) complexes [CuLX(2)] (where L = N(4) donor macrocyclic ligands) and (X = Cl(-), NO(3) (-)) have been synthesized and characterized by elemental analysis, magnetic moments, IR, EPR, mass, electronic spectra and thermal studies. The magnetic moments and electronic spectral studies suggest square planar geometry for [Cu(DBACDT)]Cl(2) and [Cu(DBACDT)](NO(3))(2) complexes and distorted octahedral geometry to the rest of the ten complexes. The biological activity of all these complexes against gram-positive and gram-negative bacteria was compared with the activity of existing commercial antibacterial compounds like Linezolid and Cefaclor. Six complexes out of twelve were found to be most potent against both gram-positive as well as gram-negative bacteria due to the presence of thio group in the coordinated ligands.     

Synthesis and thermal studies of poly(N‐acryloyl,N′‐cyanoacetohydrazide) complexes with Co(II), Fe(III), and UO2(II) ions

Polymer complexes with uranium, cobalt, and iron chlorides were synthesized and investigated by elemental analysis, electronic (uv–visible), IR vibration, and magnetic moment measurements. The thermal stabilities of N‐acryloyl,N′‐cyanoacetohydrazide (ACAH) homopolymers and polymer complexes of poly(ACAH) (PACAH) with metal chlorides were studied thermogravimetrically. The rates of polymerization of PACAH in the absence and presence of metal chlorides were studied. The activation energies of the degradation of the homopolymer and polymer complexes were calculated using the Arrhenius equation. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3354–3358, 2003     

Synthetic, Spectroscopic and Biocidal Aspects of Heterobimetallic Complexes Comprising Platinum(II) and a Group Four or Fourteen Element

Heterobimetallic complexes with varying amines have been synthesized by the reaction of [Pt(C(2)H(8)N(2))(2)]Cl(2) with group four or fourteen organometallic dichlorides, viz., R(2)MCl(2) and Cp(2)M'Cl(2) in a 1:2 molar ratio in MeOH (where M=Si or Sn, M'= Ti or Zr and R=Ph or Me). These complexes have been characterized by elemental analysis, molecular weight determinations, magnetic measurements, conductance, IR, (1)H NMR and electronic spectra. The spectral data suggest a square planar geometry for all the complexes. Conductivity data suggest that they behave as electrolytes. These monometallic precursors along with their complexes have been screened in vitro against a number of pathogenic fungi and bacteria to assess their growth inhibiting potential.     

Cationic metalloporphyrins for synthesis of conducting,water-soluble polyaniline

Catalytic oxidative polymerization of aniline was performed using the tetrapyridylporphyrin (TPyP) complexes of iron (III), manganese (III) and cobalt (III). It was found that the cationic metalloporphyrin catalyzed the polymerization of aniline more efficiently than the anionic metalloporphyrins, when using aqueous H₂O₂. The reaction was carried out in the presence of sulfonated polystyrene (SPS) as a template at different pHs, ranging from 1 to 5, and the best results were obtained at pH 2. Formation of water-soluble polyaniline (PANI) was characterized by UV–vis, FT-IR spectroscopy and cyclic voltammetry (CV). FT-IR and UV–vis spectra confirm the formation of the conducting form of PANI. Cyclic voltammetry measurements demonstrate that the polymer has convenient electroactivity.     

The DC Electrical Conductivity of the Direct Electrochemically Synthesized Poly(azomethinethiosemicarbazone)–Metal Complexes

Anodic oxidation of Co, Ni, Cu, Zn, Cd and Sn metals in an anhydrous acetone solution of poly(azomethinethiosemicarbazone) (PATS) yields the PATS–metal complexes. Chemical and thermal analyses as well as FTIR and electronic spectral data are presented to confirm the formulation of the isolated materials. The spectral data show that the ligand polymer is coordinated to the metal ions via the thiol sulfur atom and the nitrogen of the azomethine group. Thermogravimetric measurements (TGA) and differential thermal analyses (DTA) were used to obtain the energy of decomposition of PATS and its metal polymer complexes. The DC electrical conductivity measurements of PATS and the polymer complexes as annealed and 5% iodine doped forms were measured in the range 300–500 K. The products gave electrical conductivities in the semi-conducting region that increased with temperature.     

Polymer complexes: LIX. Supramolecular structural,spectral and thermal analysis of N‐[2‐(6‐aminopyridino)] acrylamide polymer complexes

Novel ligand N‐[2‐(6‐aminopyridino)] acrylamide (APA) is prepared via amidation of 2,6‐diaminopyridine with acryloyl chloride in dry benzene as solvent. The ligand is characterized on the basis of elemental analysis, infra‐red (IR) analysis and ¹H nuclear magnetic resonance. Metal–polymer complexes are reported and characterized based on elemental analysis, molar conductance, magnetic susceptibility measurements, IR, ¹H nuclear magnetic resonance, electronic spectra and thermal analysis. The molar conductance of the polymer complexes in dimethylformamide corresponds to a 1:1/1:2 electrolyte, which is non‐electrolytic. IR spectra show that polyAPA is coordinated to the metal ions in a uni‐negatively bidentate manner with N, O donor sites of azomethine N and deprotonated enolic‐O. All the polymer complexes are of high spin type. On the basis of spectral studies an octahedral geometry may be assigned for Co(II) and Ni(II) polymer complexes. The thermal stabilities of the polymer complexes were studied and the activation energies of the degradation were calculated. Copyright © 2011 Society of Chemical Industry     

Studies on polyacrylates containing pendant ligand with carbonyl and hydroxyl functions and their divalent metal complexes

A series of monomers were prepared by reacting (meth)acryloyl chloride with 2,4‐dihydroxybenzophenone, 2,4‐dihydroxybenzaldehyde, and 2,4‐dihydroxyacetophenone, respectively. The monomers were polymerized in dimethylformamide (DMF) at 70°C using benzoyl peroxide as an initiator. Polymer–metal complexes were obtained from DMF solutions of polymers with an aqueous solution of metal ions. The polymers and polymer–metal complexes were characterized by elemental analysis and spectral studies. The IR spectra of these complexes suggest that the metals are coordinated through the oxygen of the carbonyl group and the oxygen of the phenolic–OH group. The electronic spectra, electron paramagnetic resonance (EPR) spectra, and magnetic moments of polychelates showed an octahedral and square planar structure for Ni(II) and Cu(II) complexes, respectively. X‐ray diffraction studies revealed that polychelates are highly crystalline. The thermal and electrical properties, catalytic activity, and structure–property relationships are discussed. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2083–2090, 2003     

Synthesis of polymer-supported metal-ion complexes and evaluation of their catalytic activities

Polymer-supported transition-metal-ion complexes of the N,N′-bis(o-hydroxy acetophenone) propylenediamine (HPPn) Schiff base were prepared by the complexation of iron(III), cobalt(II), and nickel(II) ions on a polymer-anchored N,N′-bis(5-amino-o-hydroxy acetophenone) propylenediamine Schiff base. The complexation of iron(III), cobalt(II), and nickel(II) ions on the polymer-anchored HPPn Schiff base was 83.44, 82.92, and 89.58 wt%, respectively, whereas the unsupported HPPn Schiff base showed 82.29, 81.18, and 87.29 wt % complexation of these metal ions. The iron(III) ion complexes of the HPPn Schiff base showed octahedral geometry, whereas the cobalt(II) and nickel(II) ion complexes were square planar in shape, as suggested by spectral and magnetic measurements. The thermal stability of the HPPn Schiff base increased with the complexation of metal ions, as evidenced by thermogravimetric analysis. The HPPn Schiff base showed a weight loss of 51.0 wt % at 500°C, but its iron(III), cobalt(II), and nickel(II) ion complexes showed weight losses of 27.0, 35.0, and 44.7 wt % at the same temperature. The catalytic activity of the unsupported and supported metal-ion complexes was analyzed by the study of the oxidation of phenol and epoxidation of cyclohexene in the presence of hydrogen peroxide. The supported HPPn Schiff base complexes of iron(III) ions showed a 73.0 wt % maximum conversion of phenol and 90.6 wt % epoxidation of cyclohexene, but unsupported complexes of iron(III) ions showed 63.8 wt % conversion of phenol and 83.2 wt % epoxidation of cyclohexene. The product selectivity for catechol (CTL) and epoxy cyclohexane (ECH) was 93.1 wt % and 98.1 wt % with the supported HPPn Schiff base complexes of iron(III) ions, but it was low with the supported Schiff base complexes of cobalt(II) and nickel(II) ions. The selectivity for CTL and ECH varied with the molar ratio of the metal ions but remained unaffected by the molar ratio of hydrogen peroxide to the substrate. The energy of activation for the epoxidation of cyclohexene and oxidation of phenol with the polymer-supported Schiff base complexes of iron(III) ions was 10.0 and 12.7 kJ/mol, respectively, but it was found to be higher with the supported HPPn Schiff base complexes of cobalt(II) and nickel(II) ions and with the unsupported HPPn Schiff base complexes of iron(III), cobalt(II), and nickel(II) ions. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Photodegradation of poly(2,6-dimethyl-1,4-phenylene oxide) film with metal isopropylxanthates

The effect of metal (Co and Zn) isopropylxanthates over the range of 0.3 to 2.5% (w/w) on the photodegradation of poly(2,6-dimethyl-1,4-phenylene oxide) film was examined, by changes in the carbonyl i.r. absorption, hydroperoxide, weight average molecular weight and quantum yield of the polymer samples. The data have been processed to yield the heats of activation of the system. The photodegradation of the polymer was affected by the kind of metal, concentration of the xanthates, wavelength of irradiated light, and by the temperature. Zinc isopropylxanthate was found as a photostabilizer whereas cobalt isopropylxanthate merely enhanced the degradation. The presence of metal xanthates changed the u.v. spectra of the polymer.     

Marine coatings based on metal complexes of 4-amino-3-hydrazino-5-thio-1,2,4-triazole

Copper, cobalt, nickel and tin metal complexes of 4-amino-3-hydrazino-5-thio-1,2,4-triazole (I) have been prepared and their structure identified through IR and electronic spectra measurements. The cobalt and nickel have been found to be octahedral; on the other hand, a mixed structure is proposed for the copper complex. The complexes are incorporated in marine paint formulations in the presenceo of 4-(p-chlorobenzylideneamino)-3-(p-chlorobenzylidenehydrazino)-5-thio-1,2,4-triazole, 4-(3,4-dichlorobenzylideneamino)-3-(3,4-dichlorobenzyl idenehydrazino)-5-thio-1,2,4-triazole and 4-(p-nitrobenzylideneamino)-3-(p-nitrobenzylidenehydrazino)-5-thio-1,2,4-triazole. Each paint was applied to PVC and mild steel substrate and the panels were tested in Alexandria eastern harbour water. Paints containing copper, cobalt and nickel complexes of (I) in the presence of its chlorinated or nitro derivatives showed antifouling properties till about 4 months, while they protect steel substrate from marine corrosion for 1 month.     

Electrosynthesis and spectroelectrochemical characterization of poly(3,4-dimethoxy-thiophene), poly(3,4-dipropyloxythiophene) and poly(3,4-dioctyloxythiophene) films

Poly(3,4-dialkoxythiophene) films with different length of alkyl chain (1,3 and 8 carbon atoms) were obtained on Pt and ITO electrodes from the monomer solutions in acetonitrile by cyclic voltammetry (CV). The properties of the resulting films were studied by electrochemical methods, UV-Vis, FTIR and NMR spectra. The CVs were correlated with differential cyclic voltabsorptograms (DCVA) recorded at the absorption maxima to explain the shape of the voltammograms of the polymers studied, dependent on the alkyl-chain length in alkoxy group. The presence of the zones of different crystallinity in the polymer film was postulated. Significant influence of the type of the solvent on asymmetry of the cyclic voltammograms for the polymer doping-undoping has been discussed in terms of the solvent interaction with radical cation (polaron) delocalized on the alkoxy side groups. The polaron delocalization was proved by ¹H-NMR spectra. Appearance of infrared activated vibrations (IRAVs) in the range 1500-600 cm⁻¹ and a characteristic electronic band at 3300 cm⁻¹ at the polarization potential +0.25 V versus Ag/Ag⁺ and their gradual changes upon further polymer oxidation were interpreted in terms of evolution of different charge carriers in lightly and heavily doped polymer.