title: Predominant 1,2-insertion of styrene in the Pd-catalyzed alternating copolymerization with carbon monoxide.
abstract: The regioselectivity of styrene insertion to an acyl-Pd bond was studied by NMR in (i) a stoichiomeric reaction and (ii) a copolymerization with CO. In the stoichiometric reaction of styrene with [(CH(3)CO)Pd(CH(3)CN)[(R,S)-BINAPHOS]].[B[3,5-(CF(3))(2)C(6)H(3)](4)], both 1,2- and 2,1-products were given. To mimic the real polymerization conditions, a polyketone-substituted complex [[CH(3)(CH(2)CHCH(3)CO)(n)]Pd[(R,S)-BINAPHOS]].[B(3,5-(CF(3))(2)C(6)H(3))(4)] (n approximately 14) was prepared. When this polymer-attached Pd species was treated with styrene, the 1,2-insertion product was the only detectable species. Thus, exclusive 1,2-insertion is demonstrated to be responsible for the styrene-CO copolymerization, in sharp contrast to the predominant 2,1-insertion with conventional nitrogen ligands. Chain-end analysis revealed that beta-hydride elimination took place from the 2,1-complex but not from the 1,2-complex. Thus, once 2,1-insertion occurs, rapid beta-hydride elimination proceeds to terminate the polymerization, as is common to the other phosphorus-ligand systems. The resulting Pd-H species re-initiates the copolymerization, as was proven by MALDI-TOF mass analysis of the product copolymers.
authors.affiliation: Department of Material Chemistry, Graduate School of Engineering, Kyoto University, Sakyo-ku, Kyoto 606-8501 Japan.
authors.forename: K
authors.initials: K
authors.lastname: Nozaki
authors.forename: H
authors.initials: H
authors.lastname: Komaki
authors.forename: Y
authors.initials: Y
authors.lastname: Kawashima
authors.forename: T
authors.initials: T
authors.lastname: Hiyama
authors.forename: T
authors.initials: T
authors.lastname: Matsubara