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In this work is reported, in a first step, the effect of different experimental parameters and their relation with polymer properties using the homogeneous binary catalyst system composed by Ni( -diimine)Cl2 ( -diimine = 1,4-bis(2,6-diisopropylphenyl)-acenaphthenediimine) and {TpMs }V(Ntbu)Cl2 (TpMs = hydridobis(3-mesitylpyrazol-1-yl)(5-mesitylpyrazol-1-yl)) activated with MAO. This complexes combination produces, in a single reactor, polyethylene blends with different and controlled properties dependent on the polymerization temperature, solvent and Nickel molar fraction (xNi). In second, the control of linear low density polyethylene (LLDPE) production was possible, using a combination of catalyst precursors {TpMs}NiCl (TpMs = hydridotris(3-mesitylpyrazol-1-yl)) and Cp2ZrCl2, activated with MAO/TMA, as Tandem catalytic system. The catalytic activities as well as the polymer properties are dependent on xNi. Polyethylene with different Mw and controlled branches is produced only with ethylene monomer. Last, the application group 3 metals catalysts based, M(allyl)2Cl(MgCl2)2.4THF (M = Nd, La and Y), in isoprene polymerization with different cocatalysts systems and experimental