Group 4 Dimethylsilylenebisamido Complexes Bearing the 6-[2-(Diethylboryl)phenyl]pyrid-2-yl Motif: Synthesis and Use in Tandem Ring-Opening Metathesis/Vinyl-Insertion Copolymerization of Cyclic Olefins with Ethylene
novel ZrIV‐ and HfIV‐based bisamido complexesbearing the 6‐[2‐(diethylboryl)phenyl]pyrid‐2‐yl motif, that is, [ZrCl2Me2Si(DbppN)2}(thf)] (9) and [HfCl2Me2Si(DbppN)2}(thf)2] (10) (DbppN=6‐[2‐(diethylboryl)phenyl]pyridine‐2‐amido) have been prepared. Their reactivities have been compared with that of a model precatalyst that does not bear the aminoborane motif. Upon activation with methylalumoxane
带有6 [[2-(二乙基硼基)苯基]吡啶-2-基基序的两个基于Zr IV和Hf IV的双酰胺基配合物,即[ZrCl 2 Me 2 Si(DbppN)2 }(thf)] (9)和[HfCl 2 Me 2 Si(DbppN)2 }(thf)2 ](10)(DbppN = 6- [2-(二乙基硼基)苯基]吡啶-2-酰胺基)的制备。已经将它们的反应性与不带有氨基硼烷基序的模型预催化剂进行了比较。用甲基铝氧烷活化后,预催化剂9和10在乙烯(E)的均聚中具有活性,可生产高密度聚乙烯(HDPE)。在E与环戊烯(CPE)的共聚中,例如通过9的作用,CPE的存在导致E的聚合活性急剧增加,而CPE的掺入保持接近或为零。在9的作用下,降冰片2烯(NBE)与E的乙烯基插入共聚反应中,获得了这两种单体的统计环烯烃共聚物。然而,在较高的NBE浓度下,9导致NBE与E的可逆开环复分解(ROMP)/乙烯基插入聚合(V