Construction of coordination networks with high connectivity: a new 8-connected self-penetrating network based on tetranuclear metal clusters

Two highly connected cobalt(II) and zinc(II) coordination polymers with tetranuclear metal clusters as the nodes of network have been prepared, being the first example of an 8-connected self-penetrating net based on a cross-linked alpha-Po subnet.

Metal dependent control of cis-/trans-1,4 regioselectivity in 1,3-butadiene polymerization catalyzed by transition metal complexes supported by 2,6-bis[1-(iminophenyl)ethyl]pyridine

Fe(III), Cr(III), Fe(II), Co(II) and Ni(II) chloride complexes supported by 2,6-bis[1-(iminophenyl)ethyl]pyridine have been synthesized and characterized along with single crystal X-ray diffraction. These complexes, in combination with MAO, have been examined in butadiene polymerization. The catalytic activity and regioselectivity are strongly controlled by metal center and cocatalyst (MAO/Co ratio dependent in the case of Co(II) complex). The activity decreases in the order of Fe(III) > Co(II) > Cr(III) approximate to Ni (II) complexes, in consistent with the space around the metal center. Polybutadiene with different microstructure content, from high trans-1,4 units (88-95% for iron(III) and Cr(III)), medium trans-1,4 and cis-1,4 units (55% and 35%, respectively, for iron(II)) to high cis-1,4 units 79% for Co(II) and 97% for Ni(II) call be easily achieved by varying of the metal center.

Spectrophotometric determination of water content in alcohol organic solvents

In this work, the absorption spectral characteristics and color-change reaction mechanism of cobalt(II) chloride(COCl2) in alcohol organic solvents has been investigated in the presence of water, and then the optimum conditions for determining the water content in the solvents were selected. Results indicated that the absorption spectra Of COCl2 in alcohols decreased with the increment of water content. At the maximum absorption wavelength of 656 nm, there were good linear relationships between the logarithm of the absorbance and the water content in organic solvents such as ethanol, n-propanol, iso-propanol and n-butanol with related coefficients in the range of 0.9996 similar to 0.9998. For determining water content in organic solvents, this method is simple, rapid, sensitive, reproducible and environmentally friendly. Furthermore, the linear range cannot restrict determination of the water content in organic solvents. This method had been applied to determine the water content in ethanol and n-butanol with satisfactory recovery of water in n-butanol between 98.41%-101.29%.

Thermal and crystallization behaviors of polyethylene blends synthesized by binary late transition metal catalysts combinations

A series of reactor blends of linear and branched polyethylenes have been prepared, in the presence of modified methylaluminoxane, using a combination of 2,6-bis[1(2,6-dimethyphenylimino) pyridyl]-cobalt(II) dichloride (1), known as an active catalyst for producing linear polyethylene, and [1,4-bis(2,6-diidopropylphenyl)] acenaphthene diimine nickel(II) dibromide (2), which is active for the production of branched polyethylene. The polymerizations were performed at various levels of catalyst feed ratio at 10 bar. The linear correlation between catalyst activity and concentration of catalyst 2 suggested that the catalysts performed independently from each other. The weight-average molecular weights ((M) over bar (w)), crystalline structures, and phase structures of the blends were investigated, using a combination of gel permeation chromatography, differential scanning calorimetry, wide-angle X-ray diffraction, and small angle X-ray scattering techniques. It was found that the polymerization activities and MWs and crystallization rate of the polymers took decreasing tendency with the increase of the catalyst 2 ratios, while melting temperatures (T-m), crystalline temperatures (T,), and crystalline degrees took decreasing tendency. Long period was distinctly influenced by the amorphous component concentration.

Adsorption studies of divalent metal ions with extraction resin containing 1-hexyl-4-ethyloctyl isopropylphosphonic acid

Equilibrium distributions of cobalt(II), nickel(II), zinc(II), cadmium(II), and copper(II) have been studied in the adsorption with extraction resin containing 1-hexyl-4-ethyloctyl isopropylphosphonic acid (HEOPPA) as an extractant from chloride medium. The distribution coefficients are determined as a function of pH. The data are analyzed both graphically and numerically. The extraction of the metal ions can be explained assuming the formation of metal complexes in the resin phase with a general composition ML2(HL)(q). The adsorbed species of the metal ions are proposed to be ML2 and the equilibrium constants are calculated. The efficiency of the resin in the separation of the metal ions is provided according to the separation factors values. The separation of Zn from Ni, Cd, Cu, Co, and Co from Ni, Cd, Cu with the resin is determined to be available. Furthermore, Freundlich's isothermal adsorption equations and thermodynamic quantities, i.e., DeltaG, DeltaH, and DeltaS are determined.

Fabrication and characterization of heteropolyanion Langmuir-Blodgett films

The possibility of the formation of Langmuir-Blodgett (LB) films with dimethyldioctadecylammonium (DODA) after the addition of cobalt(II)-substituted Dawson-type tungstodiphosphate anion (briefed as (H2O)(CoP2W17O618-)-P-11) in the subphase has been explored. Marked modifications of the compression isotherms are observed when this anion is dissolved in the subphase, which demonstrates that the polyanions interact with the monolayers. LB films have been readily obtained from this system. The adsorption Fourier transform IR (FT IR) spectroscopy, atomic force microscopy (AFM), X-ray diffraction (XRD) and cyclic voltammetry (CV) have been used to investigate the morphological and molecular structure of the deposited film. The FT IR results showed the presence of the polyanion within the LB films, and the shift for its characteristic bands may be related to the presence of positively charged DODA. AFM measurement reveals that the LB films of DODA/(H2O)(CoP2W17O618)-P-II are regularly and uniformly deposited on the substrate. XRD experiments prove that the lamellar structure of the LB films of DODA/(H2O)(CoP2W17O618-)-P-II is well-defined. The LB films of DODA/(H2O)(CoP2W17O618-)-P-II immobilized onto an indium-oxide (ITO) glass, in aqueous solutions of pH 2.0-5.0, show quite facile redox reactions even for multilayers. All the experiments carried out in the present study suggest that the new materials of heteropolyanions can be formed by LB techniques and beneficial physicochemical properties of heteropolyanions can be maintained/enhanced through molecular-level design. (C) 1999 Elsevier Science S.A. All rights reserved.

Rapid automated in-situ monitoring of total dissolved iron and total dissolved manganese in underground water by reverse-flow injection with chemiluminescence detection during the process of water treatment

Measurement of iron and manganese is very important in evaluating the quality of natural waters. We have constructed an automated Fe(II), total dissolved iron(TDI), Mn(II), and total dissolved manganese(TDM) analysis system for the quality control of underground drinking water by reverse flow injection analysis and chemiluminescence detection(rFIA-CL), The method is based on the measurement of the metal-catalyzed light emission from luminol oxidation by potassium periodate. The typical signal is a narrow peak, in which the height is proportional to light emitted and hence to the concentration of metal ions. The detection limits were 3 x 10(-6) mu g ml(-1) for Fe(II) and the linear range extents up to 1.0 x 10(-4) and 5 x 10(-6) mu g ml(-1) for Mn(II) cover a linear range to 1.0 x 10(-4) mu g ml(-1). This method was used for automated in-situ monitoring of total dissolved iron and total dissolved in underground water during water treatment. (C) 1997 Elsevier Science B.V.

Two new coordination polymers of Co(II) with 1,1 '-(1,4-butanediyl)bis(benzimidazole)

Two new compounds, [CoL2(H2O)(2)](NO3)(2). 8H(2)O (1) and [CoL(H2O)(2)(CH3CO2)(2)]. H2O (2), were obtained from self-assembly of the corresponding metal salts with 1,1'-(1,4-butanediyl)bis(benzimidazole) (L). In 1, each cobalt ion is coordinated to four nitrogen atoms from four molecules of L, and to two water molecules. Metal ions are bridged by L ligands to form infinite (4, 4) networks that contain 44-membered rings. The (4, 4) networks of 1 stack in a parallel fashion, resulting in the formation of large channels in the material. In 2, each cobalt ion is coordinated to two N atoms from two L molecules, two water molecules and two carboxylate O atoms from two acetate anions. Each L molecule is coordinated to two cobalt ions, acting as a bridging ligand as in 1. The bridged cobalt ions form an infinite zigzag chain structure.

Quantitative electrochemiluminescence detection of proteins: Avidin-based sensor and tris(2,2 '-bipyridine) ruthenium(II) label

Quantitative electrochemilumineseence (ECL) detection of a model protein, bovine serum albumin (BSA) was achieved via biotin-avidin interaction using an avidin-based sensor and a well-developed ECL system of tris(2,2'-bipyridine) ruthenium(II) derivative as label and tri-n-propylamine (TPA) as coreactant. To detect the protein, avidin was linked to the glassy carbon electrode through passive adsorptions and covalent interaction with carboxylate-terminated carbon nanotubes that was used as binder to immobilize avidin onto the electrode. Then, biotinylated BSA tagged with tris(2,2'-bipyridine) ruthenium(II) label was attached to the prepared avidin surface.

Poly[[diaqua-mu-4,4 '-bipyridine-dinitratodi-mu-L-tyrosinato-dicopper(II)]: a chiral two-dimensional coordination polymer

The title compound, [Cu-2(C9H10NO3)(2)(NO3)(2)(C10H8N2)-(H2O)(2)](n), contains Cu-II atoms and L-tyrosinate (L-tyr) and 4,4'-bipyridine (4,4'-bipy) ligands in a 2:2:1 ratio. Each Cu atom is coordinated by one amino N atom and two carboxylate O atoms from two L-tyr ligands, one N atom from a 4,4'-bipy ligand, a monodentate nitrate ion and a water molecule in an elongated octahedral geometry. Adjacent Cu atoms are bridged by the bidentate carboxylate groups into a chain. These chains are further linked by the bridging 4,4'-bipy ligands, forming an undulated chiral two-dimensional sheet. O-H center dot center dot center dot O and N-H center dot center dot center dot O hydrogen bonds connect the sheets in the [100] direction. This study offers useful information for the engineering of chiral coordination polymers with amino acids and 4,4'-bipy ligands by considering the ratios of the metal ion and organic components.

A polymorph of diaquabis(pyrazine-2-carboxylato-kappa N-2(1),O)copper(II)

The title compound, [Cu(C5H3N2O2)(2)(H2O)(2)], is a new polymorph of the previously reported compound [Klein et al. (1982). Inorg. Chem. 21, 1891-1897]. The Cu-II atom, lying on an inversion center, is coordinated by two N atoms and two O atoms from two pyrazine-2-carboxylate ligands and by two water molecules in a distorted octahedral geometry with the water molecules occupying the axial sites. Intermolecular O-H center dot center dot center dot O, O-H center dot center dot center dot N and C-H center dot center dot center dot O hydrogen bonds connect the complex molecules into a two-dimensional layer parallel to (10 (1) over bar), whereas the previously reported polymorph exhibits a three-dimensional hydrogen-bonded network.

Polymerization of methyl methacrylate by iron(II) pyridinebisimine complexes

Fe(II) pyridinebisimine complexes activated with trialkylaluminium or modified methylaluminoxane (MMAO) as catalysts were employed for the polymerization of methyl methacrylate. Polymer yields, activities and polymer molecular weights as well as molecular weight distributions can be controlled over a wide range by the variation of the structures of the Fe(II) pyridinebisimine complexes and the reaction parameters such as Al/Fe molar ratio, monomer/catalyst molar ratio, monomer concentration, reaction temperature and time applied to the polymerization of methyl methacrylate. Under optimum condition, the catalytic activity of Fe(II) complex is of up to 74.5 kg(polym)/mol(Fe)h.

The synthesis and catalytic activity of poly(bis(imino)pyridyl) iron(II) metallodendrimer

The first and second generation carbosilane dendrimers with silicon hydride terminated were synthesized, and then reacted with bis(imino)pyridyl containing allyl [4-CH2==CHCH2-2,6-(Pr2C6H3N)-Pr-i==CMe(C5H3N)MeC==N(2,6-'Pr2C6H3)], in the presence of H2PtCl6 as a hydrosilylation catalyst, to afford the first and second generation carbosilane supported ligands. Complexation reactions with FeCl(2)(.)4H(2)O give rise to iron-containing carbosilane dendrimers with FeCl2 moieties bound on the periphery. The metallodendrimers were used as catalyst precursors, activated with modified methylaluminoxane, for the polymerization of ethylene. In the case of low Al/Fe molar ratio, the metallodendrimers display much higher catalytic activity towards ethylene polymerization and produce much higher molecule weight polyethylenes than the corresponding single-nuclear complex under the same conditions.

Preparation of linear alpha-olefins to high-molecular weight polyethylenes using cationic alpha-diimine nickel(II) complexes containing chloro-substituted ligands

A series of alpha-diimine nickel(II) complexes containing chloro-substituted ligands, [(Ar)N=C(C10H6)C=N(Ar)]NiBr2 (4a, Ar = 2,3-C6H3Cl2; 4b, Ar = 2,4-C6H3Cl2; 4c, Ar = 2,5-C6H3Cl2; 4d, Ar = 2,6-C6H3Cl2; 4e, Ar = 2,4,6-C6H2Cl3) and [(Ar)N=C(C10H6)C=N(Ar)](2)NiBr2 (5a, Ar = 2,3-C6H3Cl2; 5b, Ar = 2,4-C6H3Cl2; 5c, Ar = 2,5-C6H3Cl2), have been synthesized and investigated as precatalysts for ethylene polymerization. In the presence of modified methylaluminoxane (MMAO) as a cocatalyst, these complexes are highly effective catalysts for the oligomerization or polymerization of ethylene under mild conditions. The catalyst activity and the properties of the products were strongly affected by the aryl-substituents of the ligands used. Depending on the catalyst structure, it is possible to obtain the products ranging from linear alpha-olefins to high-molecular weight polyethylenes.

Self-immobilized catalysts for ethylene polymerization: neutral, single-component salicylaldiminato phenyl nickel(II) complexes bearing allyl substituents

A new family of self-immobilized ethylene polymerization catalysts, derived from neutral, single-component salicylaldiminato phenyl nickel complexes, is described.