Ligand‐Dependent Diastereoselectivity in the Palladium‐Catalyzed Copolymerization of Styrene with Carbon Monoxide

[(LL′)Pd(H₂O)](OTf)₂ complexes, in which LL′ is a chelate ligand containing the chiral 4‐benzyl‐4,5‐dihydrooxazole moiety and either pyridin‐2‐yl or 2‐(diphenylphosphino)phenyl substituents, catalyze the copolymerization of styrene with carbon monoxide with an isotactic or prevailingly syndiotactic microstructure, respectively. The chiroptical properties of the copolymers and model studies for carbon monoxide and olefin insertion on related Pd complexes suggest that the reason for the different stereochemistry of the copolymers is a site‐selective coordination of the olefin in the intermediates containing the PN ligand; a lower regioselectivity in the coordination and a different coordination site lead to the different diastereoselectivity for the copolymer formation by the complex containing the NN′‐ligand.     

Regio- and stereocontrol in the alternating copolymerization of olefins with carbon monoxide

Strictly alternating copolymers between olefins and carbon monoxide are synthesized using cationic palladium catalysts modified by phosphorus or nitrogen ligands. Basic chelate diphosphines as the ligand allow the regioregular copolymerization of aliphatic olefins thus affording, e.g. in the case of propene, poly(1-oxo-2-methyltrimethylene). Steric control of the copolymerization process towards the production of overwhelmingly isotactic copolymers is possible particularly when using atropisomeric ligands. In the case of styrene as the substrate and for all ligands employed the copolymerization process is regioregular. Prevailing syndiotactic structure is obtained with 1,10-phenanthroline or 2,2′-bipyridine as the ligand. Chelate thioether ligands allow the preparation of a completely atactic material. For 4-tert-butylstyrene an isotactic structure became accessible by using chiral bisoxazolidines. The prevailing structure of the copolymers of cyclopentene corresponds to a 1,3-enchainment of the olefin units most probably associated with a prevailing diisotactic structure