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A DFT Mechanistic Study on Ethylene Tri- and Tetramerization with Cr/PNP Catalysts: Single versus Double Insertion Pathways
Citation
Britovsek, GJP and McGuinness, DS, A DFT Mechanistic Study on Ethylene Tri- and Tetramerization with Cr/PNP Catalysts: Single versus Double Insertion Pathways, Chemistry - A European Journal, 22, (47) pp. 16891-16896. ISSN 0947-6539 (2016) [Refereed Article]
Copyright Statement
Copyright 2016 Wiley-VCH Verlag GmbH & Co.
DOI: doi:10.1002/chem.201603909
Abstract
The mechanism of ethylene trimerization and tetramerization with a chromium-diphosphinoamine (Cr-PNP) catalyst system has been studied by theoretical (DFT) methods. Two representative ligands have been explored, namely Ph2PN(Me)PPh2 and (o-MeC6H4)2PN(Me)P(o-MeC6H4)2. Calculations on the former ligand reveal how a combination of single and double ethylene insertion mechanisms may lead to 1-hexene, 1-octene and the major side products (cyclopentanes and n-alkanes). For the latter ligand, introduction of o-alkyl substitution leads to a more sterically congested active species, which suppresses the available pathways for tetramerization and side product formation. Hence, the high selectivity of o-aryl substituted PNP ligands for trimerization can be rationalized.
Item Details
Item Type: | Refereed Article |
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Keywords: | trimerisation, tetramerisation, DFT |
Research Division: | Chemical Sciences |
Research Group: | Inorganic chemistry |
Research Field: | Organometallic chemistry |
Objective Division: | Manufacturing |
Objective Group: | Industrial chemicals and related products |
Objective Field: | Organic industrial chemicals (excl. resins, rubber and plastics) |
UTAS Author: | McGuinness, DS (Dr David McGuinness) |
ID Code: | 113506 |
Year Published: | 2016 |
Funding Support: | Australian Research Council (FT100100609) |
Web of Science® Times Cited: | 33 |
Deposited By: | Chemistry |
Deposited On: | 2017-01-05 |
Last Modified: | 2017-08-29 |
Downloads: | 0 |
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