Australian Journal of Chemistry Australian Journal of Chemistry Society
An international journal for chemical science
RESEARCH ARTICLE

Ethylene Trimerisation with Cr-PNP Catalysts: A Theoretical Benchmarking Study and Assessment of Catalyst Oxidation State*

David S. McGuinness A D , Bun Chan B , George J. P. Britovsek C D and Brian F. Yates A
+ Author Affiliations
- Author Affiliations

A School of Physical Sciences – Chemistry, University of Tasmania, Private Bag 75, Hobart, Tas. 7001, Australia.

B School of Chemistry, University of Sydney, Sydney, NSW 2006, Australia.

C Department of Chemistry, Imperial College London, Exhibition Road, South Kensington, London SW7 2AZ, UK.

D Corresponding authors. Email: david.mcguinness@utas.edu.au; g.britovsek@imperial.ac.uk

Australian Journal of Chemistry 67(10) 1481-1490 https://doi.org/10.1071/CH14436
Submitted: 4 July 2014  Accepted: 28 August 2014   Published: 10 September 2014

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.


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