title: New catalyst design for polymerization of norbornene esters by reducing intramolecular interaction.
abstract: We have used density functional theory to study palladium-based catalysts commonly used for the polymerization of norbornene derivatives with an ester group. Exo-exo, exo-endo, and endo-endo isomers of catalyst complexes were investigated; the endo-endo isomer was the most stable and inactive due to an intramolecular interaction between Pd and O of the carbonyl group. Phosphine groups are effective in minimizing the Pd-O interaction in the endo-endo isomer and P(C6H11)3 was found to be the most efficient reagent. The intramolecular Pd-O interactions were estimated using model complexes, and it was demonstrated that they play a crucial role in stabilizing the endo-endo isomer.
authors.affiliation: Corporate R&D, LG Chem. Ltd., Research Park, 305-380 Daejon, South Korea. michaol@lgchem.com
authors.forename: Kyoung Hoon
authors.initials: KH
authors.lastname: Kim
authors.forename: Young-Kyu
authors.initials: YK
authors.lastname: Han
authors.forename: Sang Uuk
authors.initials: SU
authors.lastname: Lee
authors.forename: Sung-Ho
authors.initials: SH
authors.lastname: Chun
authors.forename: Jong Hoa
authors.initials: JH
authors.lastname: Ok
mesh_terms: D001643:Bridged Bicyclo Compounds / Q000737:chemistry*; D002384:Catalysis; D015195:Drug Design; D004952:Esters / Q000737:chemistry*; D007536:Isomerism; D008745:Methylation; D008968:Molecular Conformation; D011108:Polymers / Q000737:chemistry*
chemical_list: D001643:Bridged Bicyclo Compounds; D004952:Esters; D011108:Polymers