Abstract
The nature of Ni(I) species formed upon the activation of the N,N-α-diimine Ni(II) ethylene polymerization precatalyst LNiIIBr2 (1) with AlMe3 and MMAO has been studied in detail by 1H, 2H NMR, and electron paramagnetic resonance (EPR) spectroscopy (L = 1,4-bis(2,6-diisopropylphenyl)-2,3-dimethyl-1,4-diazabuta-1,3-diene). It has been shown that neutral paramagnetic NMR and EPR active heterobinuclear complexes of types LNiI(μ-Me)(μ-Br)AlR2 and LNiI(μ-Me)2AlR2 (R = Me in the case of AlMe3 and R = Me or iBu in the case of MMAO) predominate in toluene solutions of 1/AlMe3 and 1/MMAO at room temperature. The effect of the cocatalyst/catalyst ratio on the relative concentrations of LNiI(μ-Me)(μ-Br)AlR2 and LNiI(μ-Me)2AlR2 has been studied and their role in ethylene polymerization is discussed.
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