Insights into CO/styrene copolymerization by using PdII catalysts containing modular pyridine-imidazoline ligands

Continuing our studies into the effect that N-N' ligands have on CO/styrene copolymerization, we prepared new C-1-symmetrical pyridine-imidazoline ligands with 4',5'-cis stereochemistry in the imidazoline ring (5) and 4',5'-trans stereochemistry (6-10) and compared them with our previously reported ligands (1-4). Their coordination to neutral methylpalladium(II) (5a-10a) and cationic complexes (5b-10b), investigated in solution by NMR spectroscopy, indicates that both the electronic and steric properties of the imidazolines determine the stereochemistry of the palladium complexes. The crystal structures of two neutral palladium precursors [Pd(Me)(2-n)Cl-n-(N-N')] (n = 1 for 8a; n = 2 for 9a') show that the Pd-N coordination distances and the geometrical distortions in the imidazoline ring depend on the electronic nature of the substituents in the imidazoline fragment. Density functional calculations performed on selected neutral and cationic palladium complexes compare well with NMR and X-ray data. The calculations also account for the formation of only one or two stereoisomers of the cationic complexes. The performance of the cationic complexes as catalyst precursors in CO/4-tert-butylstyrene copolymerization under mild pressures and temperatures was analyzed in terms of the productivity and degree of stereoregularity of the polyketones obtained. Insertion of CO into the Pd-Me bond, which was monitored by multinuclear NMR spectroscopy, shows that the N ligand influences the stereochemistry of the acyl species formed.