Department of Chemistry, The University of Chicago, 5735 South Ellis Avenue, Chicago, IL, 60637, USA.
Permanent address: New Product R&D Center, Technology General Division, Asahi Glass Co., LTD., 1150 Hazawa-cho, Kanagawa-ku, yokohama-shi, Kanagawa, 221-8755, Japan.
Angew Chem Int Ed Engl. 2017 Feb 6;56(7):1820-1824. doi: 10.1002/anie.201611198. Epub 2017 Jan 12.
The discrete (phosphinoarenesulfonate)Pd fluoride complex (PO )PdF(lutidine), where PO =(2-MeOC H )(2-{2,6-(MeO) C H }C H )(2-SO -5-MeC H )P, inserts vinyl fluoride (VF) to form (PO )PdCH CHF (lutidine) and inserts multiple ethylene (E) units to generate polyethylene that contains -CH F chain ends. These results provide strong evidence that the -CHF and -CH F chain ends in E/VF copolymer generated by (phosphinoarenesulfonate)PdR catalysts form by β-F elimination of Pd(β-F-alkyl) species, VF or E insertion of the resulting (PO)PdF species, and subsequent chain growth. These results also imply that β-F elimination is not an important catalyst deactivation reaction in this system.
膦酸酯钯氟化物配合物(PO)PdF(三乙胺),其中 PO =(2-MeOC6H4)(2-{2,6-(MeO)C6H3}C6H3)(2-SO-5-MeC6H4)P,插入氟乙烯(VF)形成(PO)PdCHCHF(三乙胺),并插入多个乙烯(E)单元生成含有-CHF 链末端的聚乙烯。这些结果为(膦酸酯)PdR 催化剂生成的 E/VF 共聚物中的-CHF 和-CHF 链末端通过 Pd(β-F-烷基)物种的β-F 消除、生成的(PO)PdF 物种的 VF 或 E 插入以及随后的链增长形成提供了有力证据。这些结果还表明,β-F 消除不是该体系中重要的催化剂失活反应。