eCite Digital Repository
Ethylene trimerisation with Cr-PNP catalysts: a theoretical benchmarking study and assessment of catalyst oxidation state
Citation
McGuinness, DS and Chan, B and Britovsek, GJP and Yates, BF, Ethylene trimerisation with Cr-PNP catalysts: a theoretical benchmarking study and assessment of catalyst oxidation state, Australian Journal of Chemistry, 67, (10) pp. 1481-1490. ISSN 0004-9425 (2014) [Refereed Article]
Copyright Statement
Copyright 2014 CSIRO
DOI: doi:10.1071/CH14436
Abstract
A model for the homogeneous Cr-PNP (PNP = diphosphinoamine) ethylene trimerisation and tetramerisation catalyst system has been studied theoretically, with the aim of identifying suitable density functional theory methods for treatment of this catalyst, and evaluating the likely oxidation and spin states of the active species. Benchmarking studies involving high-level treatment reveal the difficulty of accurately calculating the thermochemistry of this system, and suggest that local density functionals, such as M06L, probably provide the best option. Density functional theory modelling of catalyst activation and the first steps of oligomerisation up until 1-hexene formation appears to favour a CrI–CrIII mechanism, involving spin surface crossing from sextet to quartet states.
Item Details
Item Type: | Refereed Article |
---|---|
Keywords: | chromium, catalysis, trimerization, tetramerization |
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) |
UTAS Author: | Yates, BF (Professor Brian Yates) |
ID Code: | 97337 |
Year Published: | 2014 |
Funding Support: | Australian Research Council (FT100100609) |
Web of Science® Times Cited: | 18 |
Deposited By: | Chemistry |
Deposited On: | 2014-12-11 |
Last Modified: | 2018-03-14 |
Downloads: | 0 |
Repository Staff Only: item control page