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Mechanism of ethylene dimerization catalyzed by Ti(OR')4/AlR3


Suttil, JA and McGuinness, DS, Mechanism of ethylene dimerization catalyzed by Ti(OR')4/AlR3, Organometallics, 31, (19) pp. 7004-7010. ISSN 0276-7333 (2012) [Refereed Article]

Copyright Statement

Copyright 2012 American Chemical Society

DOI: doi:10.1021/om3008508


Ti-alkoxide-based catalysts in combination with AlEt3 are responsible for the production of a significant proportion of the world's 1-butene supply, via the dimerization of ethylene. A metallacycle mechanism is normally presumed to operate with this system. However, despite its importance, the catalyst is not mechanistically well understood. The mechanism of dimerization has been studied through a series of C2H4/C2D4 co-oligomerization experiments and comparison of theoretical and experimental mass spectra. The results obtained show that the textbook metallacycle mechanism is most likely not responsible for dimerization with this catalyst. Instead, an excellent fit between the theoretical and experimental mass spectra is obtained when a conventional Cossee-type mechanism (insertion/β-hydride elimination) is modeled. The formation of both the primary product 1-butene and the secondary reaction products (ethylene/1-butene co-dimers) is best explained by this mechanism.

Item Details

Item Type:Refereed Article
Research Division:Chemical Sciences
Research Group:Inorganic chemistry
Research Field:Transition metal chemistry
Objective Division:Manufacturing
Objective Group:Industrial chemicals and related products
Objective Field:Organic industrial chemicals (excl. resins, rubber and plastics)
UTAS Author:Suttil, JA (Mr James Suttil)
UTAS Author:McGuinness, DS (Dr David McGuinness)
ID Code:81005
Year Published:2012
Web of Science® Times Cited:26
Deposited By:Chemistry
Deposited On:2012-11-21
Last Modified:2013-05-08
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