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The mechanism of ethylene dimerization with the Ti(OR')4/AIR3 catalytic system: DFT studies comparing metallacycle and Cossee proposals
journal contribution
posted on 2023-05-17, 21:30 authored by Robinson Jr, R, McGuinness, DS, Brian YatesBrian YatesThe 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.
Funding
Australian Research Council
History
Publication title
ACS CatalysisIssue
12Pagination
3006-3015ISSN
2155-5435Department/School
School of Natural SciencesPublisher
American Chemical SocietyPlace of publication
United States of AmericaRights statement
Copyright 2013 American Chemical SocietyRepository Status
- Restricted