Nickel(II) complexes of bidentate N-N′ ligands containing mixed pyrazole, pyrimidine and pyridine aromatic rings as catalysts for ethylene polymerisation

This work describes the synthesis and characterisation of Ni(II) complexes of the following neutral bidentate nitrogen ligands containing pyrazole (pz), pyrimidine (pm) and pyridine (py) aromatic rings: 2-pyrazol-1-yl-pyrimidine (pzpm), 2-(4-methyl-pyrazol-1-yl)-pyrimidine (4-Mepzpm), 2-(4-bromo-pyrazol-1-yl)-pyrimidine (4-Brpzpm), 2-(3,5-dimethyl-pyrazol-1-yl)-pyrimidine (pz*pm), 2-pyrazol-1-yl-pyridine (pzpy) and bis(3,5-dimethylpyrazol-1-yl)phenylmethane (bpz*mph). The complexes [NiBr2(pzpm)] (1), [NiBr2(4-Mepzpm)] (2), [NiBr2(4-Brpzpm)] (3), [NiBr2(pz*pm)] (4), [NiBr2(pzpy)] (5) and [NiBr2(bpz*mph)] (6) were tested as catalysts for ethylene polymerisation, in the presence of the cocatalysts methylaluminoxane (MAO) or diethylaluminium chloride (AlEt2Cl), the catalyst systems 1-3/MAO showing moderate to high activities up to the temperature of 20 °C only in the presence of MAO, whereas 4-6/MAO revealed to be inactive. Other related Pd(II) complexes, already reported in previous works, such as [PdClMe(pzpm)], [PdClMe(pz*pm)], [PdClMe(pzpy)] and [PdClMe(bpz*mph)], also showed to be inactive in the polymerisation of ethylene, when activated by MAO or AlEt2Cl. Selected samples of polyethylene products were characterised by GPC/SEC, 1H and 13C NMR and DSC, showing to be low molecular weight polymers with Mn values ranging from ca. 550 to 1500 g mol−1 and unusually low dispersities of 1.2–1.7, with total branching degrees generally varying between 2 and 12%, melting temperatures from 40 to 120 °C and crystallinities from 40 to 70%.

A systematic study of the structural and magnetic properties of Mn-, Co-, and Ni-Doped Colloidal Fe3O4 nanoparticles

A series of colloidal MxFe3-xO4 (M = Mn, Co, Ni; x = 0–1) nanoparticles with diameters ranging from 6.8 to 11.6 nm was synthesized by hydrothermal reaction in aqueous medium at low temperature (200 °C). Energy-dispersive X-ray microa-nalysis and inductively coupled plasma spectrometry confirms that the actual elemental compositions agree well with the nominal ones. The structural properties of obtained nanoparticles were investigated by using powder X-ray diffraction, Raman scattering, Mössbauer spectroscopy, and electron microscopy. The results demonstrate that our synthesis technique leads to the formation of chemically uniform single-phase solid solution nanoparticles with cubic spinel structure, confirming the intrinsic doping. Magnetic studies showed that, in comparison to Fe3O4, the saturation magnetization of MxFe3-xO4 (M = Mn, Ni) decreases with increasing dopant concentration, while Co-doped samples showed similar saturation magnetizations. On other hand, whereas Mn- and Ni-doped nanoparticles exhibits superparamagnetic behavior at room temperature, ferromagnetism emerges for CoxFe3-xO4 nanoparticles, which can be tuned by the level of Co doping.