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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
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 |
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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 |
Downloads: | 0 |
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