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Mechanistic study of ethylene tri- and tetramerisation with Cr/PNP catalysts: Effects of additional donors
journal contribution
posted on 2023-05-19, 00:40 authored by Britovsek, GJP, McGuinness, DS, Tomov, AKThe mechanism of ethylene trimerisation and tetramerisation with chromium–diphosphinoamine (Cr–PNP) catalysts has been studied by experimental and theoretical (DFT) methods. The effects of a pendant ether donor (ortho-methoxyaryl ligand substitution) and of anion coordination to the active species have been studied. In the former case, coordination of the ether donor to chromium favours 1-hexene by suppressing formation of the bis(ethylene) chromacyclopentane intermediate which is postulated to be the major route to 1-octene. The effect of anion coordination is similar and as the coordination strength increases, displacement of the anion by a second ethylene ligand becomes more difficult, again favouring trimerisation over tetramerisation. Hence, the experimentally observed effects of pendant donor coordination and changes in anion coordination strength can be rationalised.
Funding
Australian Research Council
History
Publication title
Catalysis Science and TechnologyVolume
6Issue
23Pagination
8234-8241ISSN
2044-4753Department/School
School of Natural SciencesPublisher
Royal Society of ChemistryPlace of publication
United KingdomRights statement
Copyright 2016 The Royal Society of ChemistryRepository Status
- Restricted