Analogies and Differences in Palladium-Catalyzed CO/Styrene and Ethylene/Methyl Acrylate Copolymerization Reactions

被引：26

作者：

Rosar, Vera ^{[1
]}

Meduri, Angelo ^{[2
]}

Montini, Tiziano ^{[1
]}

Fini, Francesco ^{[3
]}

Carfagna, Carla ^{[3
]}

Fornasiero, Paolo ^{[1
]}

Balducci, Gabriele ^{[1
]}

Zangrando, Ennio ^{[1
]}

Milani, Barbara ^{[1
]}

机构：

[1] Univ Trieste, Dept Chem & Pharmaceut Sci, I-34127 Trieste, Italy

[2] Univ Salerno, Dept Biol & Chem, I-84084 Fisciano, SA, Italy

[3] Univ Urbino, Dept Biomol Sci, I-61029 Urbino, Italy

来源：

CHEMCATCHEM | 2014年 / 6卷 / 08期

关键词：

alkenes; copolymerization; N ligands; palladium; homogeneous catalysis; POLAR VINYL MONOMERS; COORDINATION-INSERTION COPOLYMERIZATION; BIDENTATE NITROGEN LIGANDS; CARBON-MONOXIDE; ALTERNATING COPOLYMERIZATION; MECHANISTIC INSIGHTS; PD(II) CATALYSTS; FUNCTIONAL POLYOLEFINS; BRANCHED POLYETHYLENE; METAL CATALYSTS;

D O I：

10.1002/cctc.201402192

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

The catalytic CO/styrene and ethylene/methyl acrylate copolymerizations are compared for the first time by applying the same precatalysts. With this aim, Pd-II neutral, [Pd(CH3) Cl(N-N)], and monocationic, [Pd(CH3)(L)(N-N)][PF6] (L= CH3CN, DMSO), complexes with 1-naphthyl- and 2-naphthyl-substitued alpha-diimines with both an acenaphthene and a diazabutadiene skeleton as chelating nitrogen-donor ligands (N-N) have been studied. In the case of the complexes with the 1-naphthyl-substituted ligands, syn and anti isomers are found both in solid state and in solution. All the monocationic complexes generate active catalysts for the CO/styrene copolymerization leading to atactic or isotactic/atactic stereoblock copolymers depending on the ligand bonded to palladium. Instead, in the case of the ethylene/methyl acrylate copolymerization only the complexes with the 1-naphthyl-substituted ligands generate catalysts for this reaction.

引用

页码：2403 / 2418

页数：16

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