Mechanistic investigations of the ethylene tetramerisation reaction

被引：235

作者：

Overett, MJ

Blann, K

Bollmann, A

Dixon, JT

Haasbroek, D

Killian, E

Maumela, H

McGuinness, DS

Morgan, DH

机构：

[1] Sasol Technol Pty Ltd, R&D Div, ZA-1947 Sasolburg, South Africa

[2] Sasol Technol UK Ltd, St Andrews KY16 9ST, Fife, Scotland

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2005年 / 127卷 / 30期

关键词：

D O I：

10.1021/ja052327b

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The unprecedented selective tetramerisation of ethylene to 1-octene was recently reported. In the present study various mechanistic aspects of this novel transformation were investigated. The unusually high 1-octene selectivity in chromium-catalyzed ethylene tetramerisation reactions is caused by the unique extended metallacyclic mechanism in operation. Both 1-octene and higher 1-alkenes are formed by further ethylene insertion into a metallacycloheptane intermediate, whereas 1-hexene is formed by elimination from this species as in other reported trimerisation reactions. This is supported by deuterium labeling studies, analysis of the molar distribution of 1-alkene products, and identification of secondary co-oligomerization reaction products. In addition, the formation of two C-6 cyclic products, methylenecyclopentane and methylcyclopentane, is discussed, and a bimetallic disproportionation mechanism to account for the available data is proposed.

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页码：10723 / 10730

页数：8

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