Abstract
The catalytic activation process of the Ni-based Ziegler–Natta catalyst composed of Ni(naphthenate) 2, catalytic amount of 1,3-butadiene, BF 3·OEt 2 and AlEt 3, is spectroscopically observed by using synchrotron X-ray absorption and crystal field spectroscopies, and an optimum model of the nickel active site is proposed with the density functional theory (DFT) calculations. In the X-ray absorption near edge structure (XANES) spectrum of nickel naphthenate (NN), the position of the pre-edge at 8330.0 eV and both the strong edge and the weak pre-edge peaks indicate that NN possesses high O h symmetry and is in a divalent state. The similar XANES spectra of NNB (the mixture of NN and catalytic amount of 1,3-butadiene) and NNBF (the mixture of NNB and BF 3·OEt 2) indicate that 1,3-butadiene and BF 3·OEt 2 do not greatly disturb the coordination geometry around nickel. AlEt 3 functions as the alkylating agent in the presence of BF 3·OEt 2, and initiates 1,3-butadiene polymerization in NNBFA (the mixture of NNBF and AlEt 3) where the coordination geometry is altered from O h- to T d-like but nickel remains in a divalent oxidation state. In the absence of BF 3·OEt 2, AlEt 3 works as the reducing agent in NNBA (the mixture of NNB and AlEt 3). A single and well-defined peak at 1.62 Å is observed for NN due to the NiO shell in the phase-uncorrected Fourier-transformed (FT) EXAFS (extended X-ray absorption fine structure) spectrum of NN. A significant change in the EXAFS spectrum of NNBFA has occurred where the main peak shifts toward a higher distance with increased complexity. The complex nature of the peak at 1.75 Å indicates that the coordination feature around nickel differs from the NiO shell and the longer bonds, NiC and NiF, are formed. The NiF bond of NNBFA is confirmed by the NiF peak, −137 ppm, in the 19 F -NMR spectrum. The three main absorption bands, around 8830, 14660 and 24940 cm −1, are obtained with the crystal field spectra of NN, NNB and NNBF, which represent a typical octahedral structure of Ni(II) having three spin-allowed transition bands from 3 A 2 g ground state to the 3 T 2 g , 3 T 1 g (F) and 3 T 1 g (P) states, respectively. Heterogeneity of the Ziegler–Natta catalyst is evidenced by strong scattering in the UV-Vis region of NNBFA.
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