eCite Digital Repository

Mechanistic Investigations of the Ethylene Tetramerisation Reaction

Citation

Overett, MJ and Blann, K and Bollmann, A and Dixon, JT and Haasbroek, D and Killian, E and Maumela, H and McGuinness, DS and Morgan, DH, Mechanistic Investigations of the Ethylene Tetramerisation Reaction, Journal of the American Chemical Society, 127, (30) pp. 10723-10730. ISSN 0002-7863 (2005) [Refereed Article]

DOI: doi:10.1021/ja052327b

Abstract

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 C6 cyclic products, methylenecyclopentane and methylcyclopentane, is discussed, and a bimetallic disproportionation mechanism to account for the available data is proposed. © 2005 American Chemical Society.

Item Details

Item Type:Refereed Article
Research Division:Chemical Sciences
Research Group:Other Chemical Sciences
Research Field:Industrial Chemistry
Objective Division:Manufacturing
Objective Group:Industrial Chemicals and Related Products
Objective Field:Organic Industrial Chemicals (excl. Resins, Rubber and Plastics)
Author:McGuinness, DS (Dr David McGuinness)
ID Code:46820
Year Published:2005
Web of Science® Times Cited:171
Deposited By:Chemistry
Deposited On:2007-09-04
Last Modified:2007-09-04
Downloads:0

Repository Staff Only: item control page