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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
Keywords:trimerisation, tetramerisation, DFT
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:McGuinness, DS (Dr David McGuinness)
ID Code:113506
Year Published:2016
Funding Support:Australian Research Council (FT100100609)
Web of Science® Times Cited:4
Deposited By:Chemistry
Deposited On:2017-01-05
Last Modified:2017-08-29
Downloads:0

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