Selective dimerisation of 1-hexene mediated by aluminium alkyl chloride-activated tungsten imido complexes

Dyer, Philip W.; Hanton, Martin J.; Messinis, Antonis M.

doi:10.1039/d0cy01863e

Selective dimerisation of 1-hexene mediated by aluminium alkyl chloride-activated tungsten imido complexes

Dyer, Philip W.; Hanton, Martin J.; Messinis, Antonis M.

Authors

Professor Philip Dyer p.w.dyer@durham.ac.uk
Professor

Martin J. Hanton

Antonis M. Messinis

Abstract

The selective dimerisation of 1-hexene to dodecenes was accomplished using catalysts generated from a tungsten mono- [WCl4(NR)(thf)] or bis- [WCl2(NR)2(dme)] imido complex following activation with EtAlCl2. These catalytic systems achieve 1-hexene dimerisation with productivities of up to 3757 (mol C6)(mol W)–1 and selectivities towards the dimer fraction of 88–99 wt%. Tungsten pro-catalysts bearing imido ligands with electron donating groups give high productivity and good selectivity towards the desired methyl-branched dimers. Contrastingly, complexes with electron withdrawing imido motifs are inactive for oligomerisation, instead mediating 1-hexene isomerisation. The efficacy of different aluminium-containing activators is described, with EtAlCl2 giving the best catalytic performance at a low W:Al ratio of 8 – 20. Addition of catalyst modifiers (e.g. Oct4NCl and Et3N) is found to significantly improve the catalytic performance of the alkyl aluminium-activated olefin oligomerisation systems.

Citation

Dyer, P. W., Hanton, M. J., & Messinis, A. M. (2021). Selective dimerisation of 1-hexene mediated by aluminium alkyl chloride-activated tungsten imido complexes. Catalysis Science & Technology, https://doi.org/10.1039/d0cy01863e

Journal Article Type	Article
Acceptance Date	Nov 26, 2020
Online Publication Date	Nov 27, 2020
Publication Date	Feb 7, 2021
Deposit Date	Dec 7, 2020
Publicly Available Date	Nov 26, 2021
Journal	Catalysis Science & Technology
Print ISSN	2044-4753
Electronic ISSN	2044-4761
Publisher	Royal Society of Chemistry
Peer Reviewed	Peer Reviewed
DOI	https://doi.org/10.1039/d0cy01863e