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Mechanistic Investigations of the Ethylene Tetramerisation Reaction
journal contribution
posted on 2023-05-16, 19:50 authored by Overett, MJ, Blann, K, Bollmann, A, Dixon, JT, Haasbroek, D, Killian, E, Maumela, H, McGuinness, DS, Morgan, DHThe 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.
History
Publication title
Journal of the American Chemical SocietyVolume
127Issue
30Pagination
10723-10730ISSN
0002-7863Department/School
School of Natural SciencesPublisher
American Chemical SocietyPlace of publication
WashingtonRepository Status
- Restricted