Living Alternating Copolymerization of a Methylenecyclopropane Derivative with CO to Afford Polyketone with Dihydrophenanthrene‐1,10‐diyl Groups

Abstract

AbstractSummary: Pd complexes prepared from [PdCl(Me)(L)] (L = N‐ligands) and NaBARF catalyze the alternating copolymerization of 7‐methylenedibenzo[a,c]bicyclo[4.1.0]heptane with CO to produce the polyketone. Pd complexes with substituted 1,10‐phenanthroline ligands produce the polymer with narrow molecular weight distribution. Addition of 4‐tert‐butylstyrene to the growing polymer after consumption of the initially charged monomer, results in polymer growth to afford an AB‐type block copolyketone. A Pd complex with an optically active bisoxazoline ligand produces the optically active polymer with narrow polydispersity. The addition of DBU to a solution of polyketone converts the cis‐fused six‐membered rings into the trans‐fused rings via epimerization of the CH carbon attached to the carbonyl group.Addition of I to cationic Pd complexes catalyzes the ring‐opening copolymerization of the monomer with CO to produce the polyketone, (C(CH2)C14H10CO)n (II).imageAddition of I to cationic Pd complexes catalyzes the ring‐opening copolymerization of the monomer with CO to produce the polyketone, (C(CH2)C14H10CO)n (II).