期刊
CHEMCATCHEM
卷 7, 期 14, 页码 2255-2264出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/cctc.201500498
关键词
N ligands; palladium; polyketones; polymerization; stereochemistry
资金
- Universita degli Studi di Trieste-Finanziamento di Ateneo per progetti di ricerca scientifica-FRA
- CIRCC
Two pyrene-tagged iminopyridines (NN) were used to synthesize neutral and monocationic, palladium(II) complexes, [Pd(Me)Cl(NN)] and [Pd(Me)(MeCN)(NN)][PF6]. The monocationic complexes generated active catalysts in the CO/vinyl arene copolymerization, leading to polyketones with yields and molecular weight strongly dependent on N-N, with the ketimine catalysts one order of magnitude more productive than the aldimine counterpart. The stereochemistry of polyketones synthesized with the aldimine catalyst was found to be dependent on the vinyl comonomer: prevailingly syndiotactic copolymers were obtained for styrene, prevailingly isotactic copolymers were produced for 4-methyl styrene, and atactic macromolecules were formed for 4-tert-butyl styrene. The statistical analysis demonstrated that the control of the stereochemistry switched from enantioselective site control for 4-methyl styrene to a combination of chain-end and enantioselective site control for styrene.
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