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Homo- and copolymerization of norbornene with tridentate nickel complexes bearing o-aryloxide-N-heterocyclic carbene ligands

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Abstract

A series of new pincer-type tridentate o-aryloxide-N-heterocyclic carbene nickel complexes Ni1–Ni3 were synthesized, and the molecular structure of Ni3 was confirmed by X-ray crystallography. In comparison with the above tridentate complexes, the bidentate bis(aryloxide-NHC) nickel complex Ni4 was also synthesized. On activation with either Et2AlCl or Me2AlCl, all nickel complexes showed low activity toward norbornene (NB) homopolymerization. Surprisingly, Ni1–Ni3 catalysts exhibited moderate to high activity toward the homopolymerization (up to 3.21 × 106 g PNB (mol of Ni)−1 h−1) and copolymerization of norbornene with 1-octene (up to 1.39 × 105 g polymer (mol of Ni)−1 h−1) with B(C6F5)3 as the cocatalyst even at 100 °C, showing that tridentate nickel catalysts have high thermal stability. Notably, the tridentate Ni1–Ni3 complexes showed better activities than the corresponding bidentate bis(aryloxide-NHC) nickel complex Ni4. The obtained poly(NB-co-1-octene)s were confirmed to be vinyl-addition copolymers, which exhibited high 1-octene insertion ratio (9%–17%), good thermal stability (Td > 400 °C), high molecular weight (up to 105), and narrow molecular weight distribution (PDI ≤ 1.91).

Graphical abstract: Homo- and copolymerization of norbornene with tridentate nickel complexes bearing o-aryloxide-N-heterocyclic carbene ligands

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Publication details

The article was received on 18 Oct 2017, accepted on 21 Nov 2017 and first published on 22 Nov 2017


Article type: Paper
DOI: 10.1039/C7DT03928J
Citation: Dalton Trans., 2018, Advance Article
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    Homo- and copolymerization of norbornene with tridentate nickel complexes bearing o-aryloxide-N-heterocyclic carbene ligands

    D. Yang, J. Dong and B. Wang, Dalton Trans., 2018, Advance Article , DOI: 10.1039/C7DT03928J

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