Cationic acetylacetonate palladium complexes/boron trifluoride etherate catalyst systems for polymerization of 5-methoxycarbonylnorbornene

摘要

A simple protocol using cationic acetylacetonate palladium complexes with mono-/bidentate phosphine ligands activated with BF3 center dot OEt2 as in situ-formed catalyst for polymerization of endo/exo mixture of 5-methoxycarbonylnorbornene (activity up to 1.1.10(4) g 1 h(-1)) or 5-phenylnorbornene (7.21.0(5) g mol(-1) h(-1)), and norbomene (3.340(8) g mol(-1) h(-1)) have been developed. It was observed that the ligands nature strongly influence the catalytic activity. The catalyst system Pd(II)/BF3 center dot OEt2 was also active for the copolymerization of norbomene with 5-methoxycarbonylnorbornene. DFT calculations of isomers upon single insertion of 5-methoxycarbonylnorbornene into Pd-H bond and NMR/FTIR studies for pre-catalyst activation mechanism were performed.