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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 Yates
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.

Funding

Australian Research Council

History

Publication title

ACS Catalysis

Issue

12

Pagination

3006-3015

ISSN

2155-5435

Department/School

School of Natural Sciences

Publisher

American Chemical Society

Place of publication

United States of America

Rights statement

Copyright 2013 American Chemical Society

Repository Status

  • Restricted

Socio-economic Objectives

Organic industrial chemicals (excl. resins, rubber and plastics)

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