Chemistry of organosilicon compounds. 131. Substituent effects by deuterium and alkyl groups and carbon-13 hyperfine coupling constants of cyclopentadienyl radicals as studied by electron spin resonance
CH-Aktivierungsreaktionen an substituierten Zirconocenkomplexen und deren Verwendung in der katalytischen Ethylenpolymerisation
作者:Andrea I Licht、Helmut G Alt
DOI:10.1016/s0022-328x(03)00508-4
日期:2003.11
Zirconocene dichloride complexes with substituents containing aliphatic end groups at the aromatic ligands react with two equivalents of n-butyllithium to give metallacyclic zirconocene complexes via aliphatic CH-activation reactions. As well as ω-alkenyl substituted zirconocene dichloride complexes with terminal aliphatic groups as zirconocene dichloride complexes with purely aliphatic substituents
在芳族配体上具有包含脂族端基的取代基的二茂锆二茂合物与二当量的正丁基锂反应,通过脂族CH活化反应生成金属环茂锆茂配合物。具有末端脂族基团的ω-烯基取代的二氧化锆茂金属配合物以及具有纯脂族取代基的二氯化锆茂金属配合物也适用于此类金属环的合成。与甲基铝氧烷(MAO)结合使用时,这些金属环对于乙烯聚合而言是极好的催化剂。它们的活性可以是相应的二茂锆二氯化物离析物的活性的三倍半。催化剂25 / MAO能够生产2640 kg PE g -1 Zr h(60°C,戊烷溶液,10 bar乙烯压力)。