Copolymerization of carbon monoxide with exo‐methylenecycloalkane and dienes: synthesis of functionalized aliphatic polyketones

Synthesis of functional aliphatic polyketones was achieved by co‐ and terpolymerization of the strained exo ‐methylenecycloalkane, methylenecyclopropane (MCP), and also the dienes 1,5‐hexadiene, 1,7‐octadiene and 1,6‐heptadien‐4‐ol, with carbon monoxide and propene, using the dicationic palladium(II) phosphine complex [Pd(dppp) (NCCH 3 ) 2 ](BF 4 ) 2 (I) (dppp is 1,3‐bis(diphenyl‐phosphino)propane) as the catalyst precursor. The resulting MCP/CO copolymer contains both ring‐opened and cyclic microstructures. Ring‐opening copolymerization yields exo ‐methylene functionalized polyketone. In contrast to hexadiene/carbon monoxide copolymer (Hx/CO), no ring structures were observed in the alternating octadiene/carbon monoxide (Oc/CO) and heptadien‐4‐ol/carbon monoxide (Hp‐ol/CO) copolymers. The remaining double bonds were left intact to yield polymers with olefinic functionalities in the side chains.