Polymerization of Diazoacetates Initiated by the Pd(<i>N</i>-arylmaleimide)/NaBPh<sub>4</sub> System: Maleimide Insertion into a Pd–C Bond Preceding to Initiation Leading to Efficient α-Chain-End Functionalization of Poly(alkoxycarbonylmethylene)s
作者:Hiroaki Shimomoto、Hinano Hayashi、Kyoka Aramasu、Tomomichi Itoh、Eiji Ihara
DOI:10.1021/acs.macromol.2c00508
日期:2022.7.26
experimental observations revealed the incorporation of one N-arylmaleimide molecule coordinated on the Pd center into the α-chain end of the polymers obtained with the initiating system, indicating that the initiating species of the polymerization was generated by insertion of N-arylmaleimide into a Pd–Ph linkage, which was first formed by the reaction of the Pd(0) complex with NaBPh4, and that the initiating
三种新的基于N-芳基马来酰亚胺的 Pd(0) 配合物 [Pd( N-苯基马来酰亚胺) 2 (2,5-降冰片二烯) ( 1 ), Pd( N -2,6-二氟苯基马来酰亚胺) 2 (2,5-降冰片二烯) ( 2 ) 和 Pd( N -2,6-二氟苯基马来酰亚胺) 2 (二亚苄基丙酮) ( 3 )] 作为引发剂与NaBPh 4 [Pd( N-芳基马来酰亚胺)/NaBPh 4体系] 一起用于重氮乙酸酯的聚合. Pd( N-芳基马来酰亚胺)/NaBPh 4系统聚合了一系列重氮乙酸酯(重氮乙酸乙酯、苄基和环己基重氮乙酸酯)以产生中等至高产率的聚合物,特别是对重氮乙酸环己酯表现出高活性。基质辅助激光解吸/电离飞行时间质谱 (MALDI-TOF-MS) 分析和其他实验观察表明,将一个在 Pd 中心配位的N-芳基马来酰亚胺分子掺入所得聚合物的 α-链末端与引发系统,表明聚合的引发物质是通过将N-芳基马来酰亚胺插入