A 2D coordination polymer with brick-wall network topology based on the [Cu(NCS)(2)(pn)] monomer

The new complex [Cu(NCS)(2)(pn)] (1) (pn = 1,3-propanediamine) has been synthesized and characterized by elemental analysis, infrared and electronic spectroscopy. Single crystal X-ray diffraction studies revealed that complex 1 is made up of neutral [Cu(NCS)(2)(pn)] units which are connected by mu-1,3,3-thiocyanato groups to yield a 2D metal-organic framework with a brick-wall network topology. Intermolecular hydrogen bonds of the type NH...SCN and NH...NCS are also responsible for the stabilization of the crystal structure. (c) 2007 Elsevier B.V. All rights reserved.

Titanium and zirconium complexes containing sterically hindered hydrotris(pyrazolyl)borate ligands: synthesis, structural characterization, and ethylene polymerization studies

The synthesis, characterization and ethylene polymerization behavior of a set of Tp'MCl3 complexes (4, M = Ti, Tp' HB(3-neopentyl-pyrazolyl)(3)(-) (Tp(NP)); 5, M = Ti, Tp'= HB(3-tert-butyl-pyrazolyl)(3)(-) (Tp(tBu)); 6, M = Ti, Tp' = HB(3-phenyl-pyrazolyl)(3)(-) (Tp(Ph)); 7, M = Zr, Tp' = HB(3-phenyl-pyrazolyl)(3)(-) (Tp(ph)); 8, M = Zr, Tp' = HB(3-tert-butyl-pyrazolyl)(3)(-) (Tp(tBu))) is described. Treatment of these tris(pyrazolyl)borate Group IV compounds with methylalumoxane (MAO) generates active catalysts for ethylene polymerization. For the polymerization reactions performed in toluene at 60 degreesC and 3 atm of ethylene pressure, the activities varied between 1.3 and 5.1 X 10(3) g of PE/mol[M](.)h. The highest activity is reached using more sterically open catalyst precursor 4. The viscosity-average molecular weights ((M-v) over bar) of the PE's produced with these catalyst precursors varying from 3.57 to 20.23 x 10(5) gmol(-1) with melting temperatures in the range of 127-134 degreesC. Further polymerization studies employing 7 varying Al/Zr molar ratio and temperature of polymerization showed that the activity as well as the polymer properties are dependent on these parameters. In that case, higher activity was attained at 60 degreesC. The viscosity-average molecular weights of the polyethylene's decreases with increasing AI/Zr molar ratio. (C) 2003 Elsevier B.V. All rights reserved.

An investigation of cadmium(II) and nickel(II) adsorption by chitin graft covolymer

Chitin hydrogels of poly(vinylpyrrolidone) (VP) were prepared by means of the hydrogen peroxide graft copolymerization process. The effect of the VP grafted chain on water diffusion through the biopolymer was studied. Fourier transform infrared spectra of the VP-g-Ch showed an increase in the intensities of the hydroxyl and carbonyl stretching bands indicating a reduction in the hydrogen bonding of chitin. An investigation was undertaken regarding the adsorption of nickel(II) and cadmium(II) ions from aqueous solutions by the VP grafted chitin and the effects of the grafting degree on the Cd2+ and Ni2+ sorption were studied. The Cd2+ and Ni2+ adsorption equilibrium data correlate well with the Freundlich equation. The results indicate that the Ch-g-VP graft copolymer under investigation is a potentially powerful chelating material that can be employed for Ni2+ and Cd2+ ion removal from wastewater effluents. (C) 2004 Wiley Periodicals, Inc.

Synthesis and characterization of solid molybdenum(VI) complexes with glycolic, mandelic and tartaric acids. Photochemistry behaviour of the glycolate molybdenum complex

The complexes (NH4)(2)[ MoO2( C2H2O3)(2)]center dot H2O, (NH4)(2)[MoO2(C8H6O3)(2)] and (NH4)(2) [MoO3(C4H4O6)]center dot H2O were prepared by reaction of MoO3 with glycolic, mandelic and tartaric acids, respectively. The complexes were characterized by elemental and thermal analysis, IR spectroscopy and X- ray diffraction. Crystals of the glycolate and tartarate complexes are orthorhombic and the mandelate complex is monoclinic. Elemental and thermal analysis data showed that the glycolate and tartarate complexes are monohydrated. Hydration water is not present in the structure of the mandelate complex. IR spectra showed COO- is involved in coordination as well as the oxygen atom of the deprotonated hydroxyl group of the alpha-carbon. The glycolate molybdenum complexes with general formula M-2[MoO2(C2H2O3)(2)]center dot nH(2)O, where M is an alkali metal and n=1 or 1/2, were also prepared and characterized. Aqueous solutions of the glycolate complex become blue and mandelate and tartarate complexes change to yellow or brown when exposed to UV- radiation.

A new method for extending the range of conductive polymer sensors for contact force

This paper describes a technique for extending the force range of thin conductive polymer force sensors used for measuring contact force. These sensors are conventionally used for measuring force by changing electrical resistance when they are compressed. The new method involves measuring change in electrical resistance when the flexible sensor, which is sensitive to both compression and bending, is sandwiched between two layers of spring steel, and the structure is supported on a thin metal ring. When external force is applied, the stiffened sensor inside the spring steel is deformed within the annular center of the ring, causing the sensor to bend in proportion to the applied force. This method effectively increases the usable force range, while adding little in the way of thickness and weight. Average error for loads between 10 N and 100 N was 2.2 N (SD = 1.7) for a conventional conductive polymer sensor, and 0.9 N (SD = 0.4) using the new approach. Although this method permits measurement of greater loads with an error less than 1 N, it is limited since the modified sensor is insensitive to loads less than 5 N. These modified sensors are nevertheless useful for directly measuring normal force applied against handles and tools and other situations involving forceful manual work activities, such as grasp, push, pull, or press that could not otherwise be measured in actual work situations.

Synthesis, characterisation and thermal behaviour of solid state compounds of 4-methylbenzylidenepyruvate with some bivalent metal ions

Solid state M-4-Me-BP compounds, where M stands for bivalent Mn, Fe, Co, Ni, Cu, Zn, Pb and 4-Me-BP is 4-methylbenzylidenepyruvate, have been synthesized. Simultaneous thermogravimetry-differential thermal analysis (TG-DTA), differential scanning calorimetry (DSC), X-ray powder diffractometry, infrared spectroscopy, elemental analysis, and complexometry were used to characterise and to study the thermal behaviour of these compounds. The results led to information about the composition, dehydration, thermal stability and thermal decomposition of the isolated complexes. (C) 2002 Elsevier B.V. B.V. All rights reserved.

Combination of nickel and titanium complexes containing nitrogen ligands as catalyst for polyethylene reactor blending

Ethylene was polymerized using a combination of Ni(diimine)Cl-2 (1) (diimine = 1,4-bis(2,6-di-isopropylphenyl)-acenaphthenediimine) and {Tp(Ms)*} TiCl3 (2) (Tp(Ms)* = hydridobis(3-mesitylpyrazol-1-yl)(5-mesityl-pyrazol-1-yl)) compounds in the presence of methyl-aluminoxane (MAO) at 30 degrees C. The productivity reaches a maximum at X-Ni = 0.75 (1400 kg of PE/mol[M] . h), and the produced polyethylene (PE) showed maximal melt flow index (0.13 g/10 min) and minimal intrinsic viscosity (2.24 dL/g) compared to polyethylenes obtained with different values of nickel loading fractions (X-Ni). Productivity intrinsic viscosity data, as well as melt flow index measurements markedly depend upon the content of the late transition metal, thus suggesting a synergic effect between nickel and titanium catalysts.

Palladium(II) Complexes with Thiosemicarbazones. Syntheses, Characterization and Cytotoxicity against Breast Cancer Cells and Anti-Mycobacterium tuberculosis Activity

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

New chelate complexes of trivalent Y and lanthanides (Eu, Ho, Yb) with a triazene N-oxide: Synthesis, structural characterization and luminescence properties

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Metal carbonyls with zinciron bond: synthesis and vibrational spectra

The compounds of the type LZnFe(CO)4 (L = dien, trien, tn, s-diMeen, Meen) not yet reported and (NH3)3ZnFe(CO)4, already known, were prepared and studied by IR and Raman spectroscopy. The data obtained suggest that LZnFe(CO)4, for L = (NH3)3, dien and trien are monomers with a bipyramidal trigonal configuration around the iron atom, while for L = tn, s-diMeen and Meen the complexes are probably polymers having a center of symmetry with iron atoms octahedrally co-ordinated. © 1979.

Spectrophotometric study of binary and ternary systems involving metal ions and benzylidenepyruvates: Equilibria in aqueous solutions

The protonation of 4-dimethylaminobenzylidenepyruvate (DMBP) and 2-chloro-4-dimethylaminobenzylidenepyruvate (2-CI-DMBP) and their complex formation with Mn(II), Co(II), Ni(II), Cu(II), Zn(II), Pb(II), Cd(II) and Al(III) have been studied by potentiometric and spectrophotometric methods at 25 °C and ionic strength 0.500 M, held with sodium perchlorate. The stability order found for 1 :1 complexes of both ligands is Al(III) > Cu(II) > Pb(II) > Ni(II) > Zn(II) > Co(II) > Cd(II) > Mn(II). The stability changes move in the same direction as the pKa of the ligands. The results are compared with literature values reported for metal ion pyruvate systems. Thermodynamic stabilities of ternary complexes formed in Cu(II)-B-L- systems, where B = 2,2′-bipyridyl (bipy), ethylenediamine or glycinate and L = DMBP or 2-CI-DMBP, were also determined. The Cu(bipy)L+ species are more stable than would be expected on purely statistical grounds. The importance of the :t system associated with bipy on the enhanced stability of its mixed ligand complexes is stressed. Analytical applications of the investigated ligands are outlined.

Physico-chemical parameter correlations in the [RuCl2(CO)(L)(PPh3)2] complexes (L = N-heterocycles)

Fourteen complexes in the series [RuCl2(CO)(L)(PPh3)2] (where L = N-heterocycles) have been prepared and characterized by IR and NMR spectroscopies, and cyclic voltammetry. A good correlation is found between observed and calculated electrochemical potentials; E1/2 vs pKa or (Gp, σm for a series of similar ligands. It is now reported that the carbonyl stretching frequency, νCO, and the 13C and 31P NMR signals do not correlate well with any of the physico-chemical parameters used (E1/2, Taft's and Hammett's parameters). This behaviour is probably due to the characteristics of the Ru(II) species, which does not transmit the steric and electron donor/acceptor properties of the ligands to the carbonyl group, or because the measurements are not able to detect the effect induced by the changes in the ligand L. Indeed, good correlations are obtained when the measurements directly involve the metal centre, as is the case in the E1/2 measurements. Crystals of o[RuCl2(CO)(4-pic)(PPh3)2] are monoclinic, space group P21/n, a = 12.019(2), b = 13.825(3) and c = 22.253(3) . The structure was solved by the Patterson method and was refined by full-matrix least-squares procedure to R = 0.054 and Rw = 0.055, for 2114 reflections with I > 3σ(I). For L = 2-acetylpyridine and 2-methylimidazole, complexes with formulae [RuCl2(CO)(L)(PPh3)] · L and [RuCl2(CO)(L)2 (PPh3)], respectively, were obtained. © 1998 Elsevier Science Ltd. All rights reserved.

Adsorption and structure of copper(II) complexes on a silica gel surface chemically modified with 2-aminothiazole

The isotherms of adsorption of CuX2 (X=Cl-, Br-, ClO- 4) by silica gel chemically modified with 2-aminothiazole were studied in acetone and EtOH solutions, at 25°C. The 2-aminothiazole molecule, covalently bond to the silica gel surface, adsorbs CuX2 from solvent by forming a surface complex. At low loading, the electronic and E.S.R. spectral parameters indicate that the Cu2+ complexes have a distorted tetragonal symmetry. The d-d eletronic transition spectra show that for ClO- 4 complex, the peak of absorption do not change for any degree of metal loading whilst for Cl- and Br- complexes, the peak maxima shift to higher energy with lower metal loading. © Elsevier Science Ltd.

Tetradentate schiff base copper(II) complexes

Ten copper(II) complexes of tetradentate Schiff bases obtained by condensing two moles of an o-hydroxyphenylcarbonyl compound with a diamine have been prepared and characterized by elemental analyses, melting points, IR and electronic spectra. The IR and electronic spectra of the free ligand and the complexes are compared and discussed. The deconvolution of the visible spectra of the complexes in CHCl3, approximately C2v or C1, yielded four peaks at ca. 15000, 17000, 18000-19000, and 20000-22000 cm-1, assigned to the four d-d transitions.

Crystallographic and spectroscopic studies on palladium(II) complexes containing pyrazole and thiocyanate ligands

Mononuclear palladium(II) complexes containing both pyrazole-type ligands and thiocyanate, of general formula [Pd(SCN) 2(L) 2] {L = pyrazole (HPz) and l-phenyl-3-methylpyrazole (phmPz)} have been prepared and characterized by elemental analysis, i.r. and n.m.r. spectroscopy and by single crystal X-ray diffraction methods. The Pd atom in these structures lies on the crystallographic inversion center; in a square-planar coordination geometry made by two sulfur and two nitrogen atoms of the ligands, both in trans positions.