Subtle Balance of Steric and Electronic Effects for the Synthesis of Atactic Polyketones Catalyzed by Pd Complexes with Meta-Substituted Aryl-BIAN Ligands

Both symmetric and nonsymmetric bis(aryl)acenaphthenequinonediimine ligands, featured by substituents in meta-positions of the aryl rings, have been applied for the first time as ancillary ligands for the palladium-catalyzed CO/vinyl arene copolymerization. The nature and the number of substituents affect both the productivity and the molecular weight of the synthesized copolymers. Palladium complexes containing the nonsymmetric ligands are the most efficient catalysts reported so far for the synthesis of atactic polyketones.