Pd(II) complexes bearing di- and monochelate fluorinated β-ketonaphthyliminato ligand and their catalytic properties towards vinyl-addition polymerization and copolymerization of norbornene and ester-functionalized norbornene derivative

Fluorinated β-ketonaphthyliminate ligand CF3C(O)CHC[HN(naphthyl)]CH3 (L1) and Pd(II) complexes with dichelate fluorinated β-ketonaphthyliminato ligand, {CF3C(O)CHC[N(naphthyl)]CH3}2Pd (C1), as well as with monochelate fluorinated β-ketonaphthyliminato ligand, {CF3C(O)CHC[N(naphthyl)]CH3}Pd(CH3)(PPh3) (C2), were synthesized and their solid-state structures were confirmed using X-ray crystallographic analysis. The Pd(II) complexes were employed as precursors to catalyze norbornene (NB) homo- and copolymerization with ester-functionalized NB derivative using B(C6F5)3 as a co-catalyst. High activity up to 2.3 × 105 gpolymer molPd−1 h−1 for the C1/B(C6F5)3 system and 3.4 × 106 gpolymer molPd−1 h−1 for the C2/B(C6F5)3 system was exhibited in NB homopolymerization. Moreover, the Pd(II) complexes exhibited a high level of tolerance towards the ester-functionalized MB monomer. In comparison with the C1/B(C6F5)3 system, the C2/B(C6F5)3 system exhibited better catalytic property towards the copolymerization of NB with 5-norbornene-2-carboxylic acid methyl ester (NB-COOCH3), and soluble vinyl-addition-type copolymers were obtained with relatively high molecular weights (3.6 × 104–7.5 × 104 g mol−1) as well as narrow molecular weight distributions (1.49–2.15) depending on the variation of monomer feed ratios. The NB-COOCH3 insertion ratio in all copolymers could be controlled in the range 2.8–21.0 mol% by tuning a content of 10–50 mol% NB-COOCH3 in the monomer feed ratios. Copolymerization kinetics were expressed by the NB and NB-COOCH3 monomer reactivity ratios: rNB-COOCH3 = 0.18, rNB = 1.28 were determined for the C1/B(C6F5)3 system and rNB-COOCH3 = 0.19, rNB = 3.57 for the C2/B(C6F5)3 system using the Kelen–Tudos method. Copyright © 2014 John Wiley & Sons, Ltd.

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