Platinum(II), palladium(II) and nickel(II) complexes with N-allyl-N¢-pyrimidin-2-ylthiourea were synthesized in 1:1 and 1:2 [metal:ligand] stoichiometric ratios and characterized by elemental analyses, molar conductivities, magnetic susceptibilities and by i.r., u.v.-vis., 1 H-and 13 C-n.m.r. and mass spectra. The 1 H-and 13 C-n.m.r. chemical shifts reveal coordination of one pyrimidine-N and sulphur atoms to Pt II and Pd II . The i.r. spectra indicate that the ligand behaves as a neutral monodentate towards Ni II ; coordinates via a pyrimidine-N and as a bidendate towards Pd II and Pt II coordinates via thione-S and a pyrimidine-N. The magnetic moments and electronic spectral data suggest a square-planar geometry for Pt II and Pd II complexes, a mixture of square-planar and tetrahedral geometries for the tetracoordinate Ni II complex and octahedral for the six-coordinate one. The E.I. mass spectra of the complexes showed some isotope ion peaks of [M] + and fragments containing metals; assignments of fragments containing metal ions were supported by the appearance of their peaks among isotope clusters.
Four of the coordination compounds of the general formula, [M(DPPP)(APY)(H2O) Cl2].xH2O, where M = Ni(II), Cu(II), Mn(II), and Fe(II) and x = 0, 1, or 2 molecules of H2O, DPPP = 1,3-bis(diphenylphosphino)propane, and APY = 2-aminopyridine, have been prepared and characterized. The structure of the complexes has been confirmed by elemental analysis, FT-IR, and UV-Vis spectral data. Thermal analysis (thermogravimetry, derivative thermogravimetry, and differential thermal studies) has been used to study the thermal decomposition stages. Biological activity of all synthesized complexes was tested against five bacterial strains and three fungal strains. Bacteria and fungi strains are common contaminants of the environment in Saudi Arabia, some of which are frequently reported from contaminated water, soil, and food.
In aqueous alkaline medium, the kinetics of oxidation of methylaminopyrazole formamidine (MAPF) by hexacyanoferrate(III) (HCF)has been studied spectrophotometrically under the conditions, MAPF >> HCF at a constant ionic strength of 0.1 mol dm-3 and at 25°C. The reaction showed first order dependence on [HCF] while it exhibited fractional-first order kinetics with respect to [MAPF] and [OH-]. The oxidation rate increased with increasing ionic strength and dielectric constant of the reaction medium. Addition of small amounts of some divalent transition metal ions accelerates the oxidation rate and the order of catalytic efficiency was: Cu(II) > Ni(II) > Zn(II) > Co(II) > Cd(II). The suggested mechanism involves formation of a 1: 1 intermediate complex between HCF and the deprotonated MAPF species in a pre-equilibrium step. The final oxidation products were identified as methylaminopyrazole, dimethylamine and carbon dioxide. The appropriate rate law was deduced. The reaction constants involved in the mechanism were evaluated. The activation and thermodynamic parameters were determined and discussed.
A series of heterogeneous catalysts was prepared by doping zinc oxide with different palladium loadings in the range of 0.5%-1.5%. The prepared catalysts were characterized by SEM, TEM and XRD. These catalysts were applied to study the degradation of Methyl tert-Butyl Ether (MTBE). An amount of 100 mg of each of these catalysts was added to an aqueous solution of 100 ppm of MTBE. The resulting mixtures were irradiated with UV light for a period of 5 h. A 99.7% removal of MTBE was achieved in the case of the zinc oxide photocatalyst particles doped with 1% Pd. The photoreaction was found to be a first-order one.
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