Synthesis, crystal structure, spectroscopic and electrochemical characterization of the dinuclear complex {tetra-mu-[(+/-)-2-(p-methoxyphenoxy)-propionato-O,O']bis(aqua)dicopper(II)}

Structural, electrochemical and spectroscopic data of a new dinuclear copper(II) complex with (+/-)-2-(p- methoxyphenoxy) propionic acid are reported. The complex {tetra-mu-[(+/-)-2-(p-methoxyphenoxy)propionato-O,O']-bis( aqua) dicopper(II)} crystallizes in the monoclinic system, space group P2(1)/n with a = 14.149(1) angstrom, b = 7.495(1) angstrom, c = 19.827(1) angstrom, beta = 90.62(1) and Z = 4. X-ray diffraction data show that the two copper(II) ions are held together through four carboxylate bridges, coordinated as equatorial ligands in square pyramidal geometry. The coordination sphere around each copper ion is completed by two water molecules as axial ligands. Thermogravimetric data are consistent with such results. The ligand has an L' type shape due to the angle formed by the beta-carbon of the propionic chain and the linked p-methoxyphenoxy group. This conformation contributes to the occurrence of a peculiar structure of the complex. The complex retains its dinuclear nature when dissolved in acetonitrile, but it decomposes into the corresponding mononuclear species if dissolved in ethanol, according to the EPR measurements. Further, cyclic voltammograms of the complex in acetonitrile show that the dinuclear species maintains the same structure, in agreement with the EPR data in this solvent. The voltammogram shows two irreversible reduction waves at E-pc = -0.73 and -1.04 V vs. Ag/AgCl assigned to the Cu(II)/ Cu(I) and Cu(I)/Cu degrees redox couples, respectively, and two successive oxidation waves at E-pa = -0.01 and +1.41 V vs. Ag/AgCl, assigned to the Cu degrees/Cu(I) and Cu( I)/Cu( II) redox couples, respectively, in addition to the oxidation waves of the carboxylate ligand.

Electrochemistry of organometallic compounds. Part IV. Oxidations of benzylic derivatives and p-substituted benzylic derivatives of bis(dimethylglyoximato) and bis(salicylaldehyde)o-phenylenediimine cobalt(III) in dimethylformamide

The electrochemical oxidation of some p-substituted benzylic derivatives of Co(III) dimethylglyoximato and Co(III)bis(salicylaldehydc)o-phenylenediimine in dimethylformamide. 0.2 M in tetraethyammonium perchlorate, on a platinum electrode, at several temperatures, is described as an ECE type, the first electrochemical step being a quasi-reversible one-electron charge transfer at room temperature. At temperatures around -20°C, or lower, the influence of the irreversible chemical decomposition of the oxidized species, via a solvent or other nucleophilic-assisted reaction, is negligible. It is suggested that at low temperatures the oxidation to the formally CoIV-R species is followed by an isomerization reaction in which this complex is partially transformed in a CoIII-(R) species or a s π-complex which undergoes an electroreduction at less positive potentials than those corresponding to the reduction of the CoIV-R species. © 1982.

Thermal study of nickel(II) pyrazolyl complexes

The thermal behavior of the pyrazolyl complexes [NiCl2(HPz) 4] (1), [Ni(NCS)2(HPz)4] (2), [NiCl 2(HdmPz)4]·2H2O (3) and [Ni(NCS) 2(HdmPz)4]·2H2O (4) (HPz=pyrazole, HdmPz=3,5-dimethylpyrazole) has been studied by thermogravimetry (TG) and differential thermal analysis (DTA). The TG data indicated that the thermal stability of [NiX2(HL)4] (X=Cl, NCS) compounds varies depending on the pyrazolyl ligand in the following order HL=HPz>HdmPz. From the thermal decomposition of 3 and 4 it was possible to isolate the intermediate compounds [Ni(μ-Cl)2(HdmPz)2] (3a) and [Ni(μ-1,3-NCS) 2(HdmPz)2] (4a), respectively. The final products of the thermal decompositions of 1-4 were identified as NiO by X-ray powder diffraction. © 2005 Akadémiai Kiadó, Budapest.

Molecular and crystal structure of trans-(dicyanato)-bis(triphenylphosphine)palladium(II)

The triphenylphosphine (PPh3) displaces the acetonitrile from [PdCl2(CH3CN)2], and subsequent addition of the potassium cyanate causes substitution of the chloro ligand by NCO- to yield trans-[Pd(NCO)2(PPh3)2]. The complex was characterized by elemental analysis, IR spectroscopy and single-crystal X-ray diffraction. The title compound was crystallized in a triclinic system, space group P1 with a = 9.213(3)Å, b = 9.781(7)Å, c = 10.483(5)Å, α = 111.39(5)°, β = 93.49(3)°, γ = 103.81(4)°, V = 845.0(1)Å3, Z = 1. The coordination geometry around Pd(II) in this complex is nearly square-planar, with the ligands in a trans relationship. 2008 © The Japan Society for Analytical Chemistry.

Sensor for diuron quantitation based on the P450 biomimetic catalyst nickel(II) 1,4,8,11,15,18,22,25-octabutoxy-29H,31H-phthalocyanine

A biomimetic sensor based on a carbon paste electrode modified with the nickel(II) 1,4,8,11,15,18,22,25-octabutoxy-29H,31H-phthalocyanine complex was developed as a reliable alternative technique for the sensitive and selective analysis of the herbicide diuron in environmental media. The sensor was evaluated using cyclic voltammetry and amperometric techniques. The best amperometric responses were obtained at 750 mV vs. Ag/AgCl (KClsat), using 0.1 mol L-1 phosphate buffer solution at pH 8.0. Under these conditions, the sensor showed a linear response for diuron concentrations between 9.9 × 10-6 and 1.5 × 10-4 mol L -1, a sensitivity of 22817 (±261) μA L mol-1, and detection and quantification limits of 6.14 × 10-6 and 2 × 10-5 mol L-1, respectively. The presence of the nickel complex in the carbon paste improved selectivity, stability, and sensitivity (which increased 700%), compared to unmodified paste. The applicability of the sensor was demonstrated using enriched environmental samples (river water and soil). © 2012 Elsevier B.V. All rights reserved.

Poly [1,1'-bis(ethynyl)-4,4'-biphenyl(bis-tributylphosphine)Pt(II)] solutions used as low dose ionizing radiation dosimeter

In this work, the effect of gamma radiation on the optical properties of polymetallayne poly[1,1'-bis(ethynyl)-4,4'-biphenyl(bis-tributylphosphine)Pt(II) ] (Pt-DEBP) in chloroform solution is studied. The samples were irradiated at room temperature with doses from 0.01 Gy to 1 Gy using a 60Co gamma ray source. A new band at 420 nm is observed in the emission spectra, in superposition to the emission maximum at 398 nm, linearly dependent on dose. We propose to use the ratio of the emission amplitude bands as the dosimetric parameter. This method proved to be robust, accurate, and can be used as a dosimeter in medical applications. © 2013 AIP Publishing LLC.

Determination of Glycerol in Biodiesel Using a Nickel(II) Oxyhydroxide Chemically Modified Electrode by Cyclic Voltammetry

A glassy carbon electrode chemically modified with nickel oxyhydroxide from a nickel hexacyanoferrate (NiHCF) film was used to determine glycerol in biodiesel by cyclic voltammetry. The modified electrode exhibited a linear response to glycerol concentration in the range from 0.05 to 0.35mmol L-1, and a detection limit of 0.030mmol L-1. The glycerol concentration found in the biodiesel sample was 0.156mmol L-1. The method developed in this study showed a recovery of (100.3±5.0)%. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Copper(II) and Nickel (II) Complexation Capacity of Dissolved Organic Matter from Rivers of Agricultural and Urban Areas in the State of Sao Paulo

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

Simple and direct potentiometric determination of potassium ions in biodiesel microemulsions at a glassy carbon electrode modified with nickel(II) hexacyanoferrate nanoparticles

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

Synthesis and characterization of alpha-nickel (II) hydroxide particles on organic-inorganic matrix and its application in a sensitive electrochemical sensor for vitamin D determination

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

Electropolymerization using binuclear nickel(II) Schiff base complexes bearing N4O4 donors as supramolecular building blocks

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

Thermal analysis of coordination compounds. Part 1. Thermodecomposition of nickel(II) triphenylphosphine complexes with halides, nitrate, and thiocyanate

The compounds [NiX 2(PPh 3) 2] (where X is Cl -, Br -, I -, NO - 3, NCS -; and PPh 3 is triphenylphosphine) were prepared and characterized by infrared and atomic absorption spectroscopies and by carbon and hydrogen analyses. Simultaneous thermogravimetric (TG) and derivative thermogravimetric (DTG) curves of these complexes were recorded in air. The decrease in mass observed indicates conversion of the complexes to oxides. The thermal decomposition of the halogen and nitrate complexes occurred in a number of steps; the thiocyanate complex decomposed in a single step. © 1994.

Correlation between i.r. spectra and thermal decomposition of cobalt(II), nickel(II), copper(II) and mercury(II) complexes with piperidinedithiocarbamate and pyrrolidinedithiocarbamate

The thermal decomposition of pyrrolidinedithiocarbamate and piperidinedithiocarbamate complexes of CoII, NiII, CuII and HgII have been studied by thermogravimetry and differential scanning calorimetry. The decomposition intermediates and final products were identified by their X-ray diffraction patterns. The i.r. spectra are discussed in terms of the thermal decomposition pathways.

VIBRATIONAL ANALYSIS OF COORDINATION COMPOUNDS OF NICKEL (II): AN APPROACH TO THE TEACHING OF POINT GROUPS

VIBRATIONAL ANALYSIS OF COORDINATION COMPOUNDS OF NICKEL (II): AN APPROACH TO THE TEACHING OF POINT GROUPS. This paper presents an IR and Raman experiment executed during the teaching of the course "Chemical Bonds" for undergraduated students of Science and Technology and Chemistry at the Federal University of ABC, in order to facilitate and encourage the teaching and learning of group theory. Some key aspects of this theory are also outlined. We believe that student learning was more significant with the introduction of this experiment, because there was an increase in the discussions level and in the performance during evaluations. This work also proposes a multidisciplinary approach to include the use of quantum chemistry tools.