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A DFT mechanistic study on ethylene tri- and tetramerization with Cr/PNP catalysts: single versus double insertion pathways
File | Description | Size | Format | |
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Manuscript.docx | Accepted version | 2.48 MB | Microsoft Word | View/Open |
Title: | A DFT mechanistic study on ethylene tri- and tetramerization with Cr/PNP catalysts: single versus double insertion pathways |
Authors: | 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. |
Issue 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 General Chemistry 03 Chemical Sciences |
Publication Status: | Published |
Conference Place: | Germany |
Appears in Collections: | Chemistry Catalysis and Advanced Materials Faculty of Natural Sciences |