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The mechanism of ethylene dimerization with the Ti(OR')4/AIR3 catalytic system: DFT studies comparing metallacycle and Cossee proposals

Citation

Robinson Jr, R and McGuinness, DS and Yates, BF, The mechanism of ethylene dimerization with the Ti(OR')4/AIR3 catalytic system: DFT studies comparing metallacycle and Cossee proposals, ACS Catalysis, 3, (12) pp. 3006-3015. ISSN 2155-5435 (2013) [Refereed Article]

Copyright Statement

Copyright 2013 American Chemical Society

DOI: doi:10.1021/cs4006875

Abstract

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 Details

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:16
Deposited By:Chemistry
Deposited On:2014-01-28
Last Modified:2014-06-26
Downloads:0

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