联吡啶-钯催化一氧化碳与苯乙烯共聚的反应机理研究.docVIP

  A DFT Investigation of the Mechanism for Alternating Copolymerization of Styrene with Carbon Monoxide  5 10 15 20 25 30 35 40 45 Catalyzed by Pd(II) Complexes# Zhang Zidan1, He Xuehao2, Jiang Shichun3** (1. Department of Polymer Science and Engineering, School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072; 2. Department of Chemistry, School of Science, Tianjin University, TianJin, 300072; 3. School of Material Science Engineering, Tianjin University, TianJin 300072) Abstract: Density functional theory has been employed to study the homogeneous catalytic copolymerization of styrene with carbon monoxide. The copolymerization reaction is catalyzed by Pd(II) coordinated with 2,2’-bipyridine, a conventional nitrogen-containing bidentate ligand with achiral C2v symmetry. The chain propagation mechanism for the alternating copolymerization as well as the side reactions, including multiple insertions of CO and homopolymerization of styrene, has been investigated. This study focused exclusively on regioisomerism and stereoisomerism. We have demonstrated that the strictly alternating copolymerization is kinetically and thermodynamically favored over the side reactions (i.e., multiple insertions of CO and homopolymerization of styrene). The regiochemistry study indicates the 2,1 type. Furthermore, the stereochemistry study shows that the syndiotactic conformation is preferred over the isotactic or atactic conformations. Key words: DFT; CO; Styrene; Polyketone; Mechanism 1 Introduction Over the past decades, copolymerization of olefins (e.g., ethylene, styrene, p-methylstyrene) with carbon monoxide has absorbed many interests of researchers, due to their unusual properties either from an academic point of view or from a industrial point of view.[1] This class of copolymerizations catalyzed by cationic Pd(II) complexes with bidentate ligands produces alternating copolymers with regular stereochemistry and regiochemistry. Palladium(II) complex