Nickel and palladium complexes bearing new diarylamido-based unsymmetrical [NNN] and [SNN] pincer ligands were synthesized and tested for the polymerization of norbornene. Upon the activation of MAO, all the palladium complexes showed high catalytic activities for the vinyl-addition polymerization of norbornene up to 5.32 × 10 g of PNB (mol of Pd) h, while the corresponding nickel complexes exhibited unsatisfactory catalytic activities. Besides the usual steric and electronic effects, the sidearm effects of quinolino ([NNN] ligands) and phenylthio ([SNN] ligands) moieties have also exhibited obvious influence on the catalytic performance for the polymerization of norbornene and were further studied by density functional theory (DFT) calculations.
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