The mechanism of ethylene dimerization to 1-butene, as promoted by the Ti(OR')₄/AlR₃ catalyst system, has been explored with the aid of density functional theory (DFT) to determine which mechanistic proposal, metallacycle or Cossee-Arlman, is most likely. The theoretical studies predict that the Cossee mechanism has the lowest rate-determining reaction barrier and also that this mechanism is more likely to lead to selective dimerization. In contrast, for the metallacycle mechanism, a higher likelihood of 1-hexene formation is predicted. The possibility of isomerization or codimerization of 1-butene has also been studied according to a Cossee mechanism, with the results obtained in good agreement with previous experiments. As a result of this study and recent experimental results, a Cossee mechanism of dimerization with this catalyst, proceeding via a titanium-hydride intermediate, is considered the most probable route.

Item Type:	Refereed Article
Keywords:	dimerisation, titanium, catalysis, theoretical
Research Division:	Chemical Sciences
Research Group:	Other Chemical Sciences
Research Field:	Organometallic Chemistry
Objective Division:	Manufacturing
Objective Group:	Industrial Chemicals and Related Products
Objective Field:	Organic Industrial Chemicals (excl. Resins, Rubber and Plastics)
Author:	Robinson Jr, R (Dr Robert Robinson)
Author:	McGuinness, DS (Dr David McGuinness)
Author:	Yates, BF (Professor Brian Yates)
ID Code:	88317
Year Published:	2013
Funding Support:	Australian Research Council (FT100100609)
Web of Science® Times Cited:	17
Deposited By:	Chemistry
Deposited On:	2014-01-28
Last Modified:	2014-06-26
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