A DFT mechanistic study on ethylene tri- and tetramerization with Cr/PNP catalysts: single versus double insertion pathways

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Title: A DFT mechanistic study on ethylene tri- and tetramerization with Cr/PNP catalysts: single versus double insertion pathways
Author(s): Britovsek, GJ
McGuinness, DS
Item Type: Journal Article
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 Ph2 PN(Me)PPh2 and (o-MeC6 H4 )2 PN(Me)P(o-MeC6 H4 )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.
Publication Date: 10-Oct-2016
Date of Acceptance: 16-Aug-2016
URI: http://hdl.handle.net/10044/1/41536
DOI: https://dx.doi.org/10.1002/chem.201603909
ISSN: 0947-6539
Publisher: Wiley
Start Page: 16891
End Page: 16896
Journal / Book Title: Chemistry - A European Journal
Volume: 22
Issue: 47
Copyright Statement: © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim. This is the accepted version of the following article which has been published in final form at: http://onlinelibrary.wiley.com/doi/10.1002/chem.201603909/abstract;jsessionid=
Keywords: Science & Technology
Physical Sciences
Chemistry, Multidisciplinary
Chemistry
chromium
homogeneous catalysis
oligomerization
tetramerization
trimerization
ZETA-VALENCE QUALITY
ALPHA-OLEFINS
ETHENE TRIMERIZATION
CHROMIUM CATALYSTS
THERMAL-DECOMPOSITION
BASIS-SETS
OLIGOMERIZATION
POLYMERIZATION
METALLOCYCLES
LIGANDS
chromium
homogeneous catalysis
oligomerization
tetramerization
trimerization
General Chemistry
03 Chemical Sciences
Publication Status: Published
Conference Place: Germany
Appears in Collections:Chemistry
Catalysis and Advanced Materials
Faculty of Natural Sciences



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