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Vinyl Polymerization of Norbornene on Nickel Complexes with Bis(imino)pyridine Ligands Containing Electron-Withdrawing Groups

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journal contribution
posted on 13.02.2012, 00:00 by Artem A. Antonov, Nina V. Semikolenova, Vladimir A. Zakharov, Wenjuan Zhang, Youhong Wang, Wen-Hua Sun, Evgenii P. Talsi, Konstantin P. Bryliakov
A series of novel bis­(imino)­pyridine nickel­(II) dichloride complexes, with the bis­(imino)­pyridine ligands containing electron-withdrawing groups (F, Cl, Br, CF3), have been prepared and characterized by elemental analysis and NMR spectroscopy. All complexes exhibit paramagnetically shifted 1H NMR spectra, indicative of the high-spin (S = 1) state of the d8 nickel­(II) central atom. These complexes have been found to be highly active catalysts of vinyl-type norbornene polymerization upon activation with MAO, displaying activities up to 1.16 × 107 g of PNB (mol of cat.)−1 h–1 (the highest ever reported for norbornene polymerizations on bis­(imino)­pyridine nickel complexes) and yielding high-molecular-weight polynorbornene (Mw up to 4.5 × 106). X-ray structures for some of the nickel complexes are reported.