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Ethylene trimerisation with Cr-PNP catalysts: a theoretical benchmarking study and assessment of catalyst oxidation state

journal contribution
posted on 2023-05-18, 05:50 authored by McGuinness, DS, Chan, B, Britovsek, GJP, Brian YatesBrian Yates
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.

Funding

Australian Research Council

History

Publication title

Australian Journal of Chemistry

Volume

67

Issue

10

Pagination

1481-1490

ISSN

0004-9425

Department/School

School of Natural Sciences

Publisher

CSIRO Publishing

Place of publication

150 Oxford St, Po Box 1139, Collingwood, Australia, Victoria, 3066

Rights statement

Copyright 2014 CSIRO

Repository Status

  • Restricted

Socio-economic Objectives

Organic industrial chemicals (excl. resins, rubber and plastics)

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    University Of Tasmania

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