Synthesis, characterisation, and polymerisation studies of hexamethylindenyl zirconocenes and hafnocenes

被引：17

作者：

Arnold, Thomas A. Q. ^{[1
]}

Buffet, Jean-Charles ^{[1
]}

Turner, Zoe R. ^{[1
]}

O'Hare, Dermot ^{[1
]}

机构：

[1] Univ Oxford, Dept Chem, Chem Res Lab, Oxford OX1 3TA, England

来源：

JOURNAL OF ORGANOMETALLIC CHEMISTRY | 2015年 / 792卷

关键词：

Metallocene; Zirconium; Hafnium; Indenyl; Benzyl; Polymerisation; APPROXIMATE COULOMB POTENTIALS; ZETA VALENCE QUALITY; AUXILIARY BASIS-SETS; X-RAY-DIFFRACTION; METALLOCENE CATALYSTS; CRYSTAL-STRUCTURES; OLEFIN POLYMERIZATION; CORRELATION-ENERGY; TRANSITION-METALS; COMPLEXES;

D O I：

10.1016/j.jorganchem.2015.01.019

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

A family of group 4 metallocene complexes based on the hexamethylindenyl ligand (C9Me6H; Ind(#)) have been prepared and fully characterised. The complexes rac-Ind(2)ZrCl2 (rac-1), meso-Ind(2)(#)ZrCl(2) (meso-1), rac-Ind(2)HfCl(2) (rac-2), meso-Inq HfCl2 (meso-2) were prepared by the reaction of Ind Li with the corresponding MCI4 (where M = Zr, HO; and rac-In4Zr(CH2Ph)2 (rac-3) was derived from rac-1 using two equivalents of potassium benzyl (KCH2Ph). All five species were characterised by NMR spectroscopy, single crystal X-ray diffraction and studied using density functional theory. The zirconocenes were tested for their activity as solution-phase ethylene polymerisation catalysts and rac-1 was found to outperform the meso-1 at most temperatures. The benzyl analogue, rac-3, peaked at more than double the activity reported for the dihalide species. (C) 2015 Elsevier BY. All rights reserved.

引用

页码：55 / 65

页数：11

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