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Insertion and isomerisation of internal olefins at alkylaluminium hydride: catalysis with zirconocene dichloride
journal contribution
posted on 2023-05-18, 16:13 authored by Weliange, NM, McGuinness, DS, Michael GardinerMichael Gardiner, Patel, JThe insertion of internal olefins (hydroalumination) and chain walking isomerisation at di-n-octylaluminium hydride [Al(Oct)2H], promoted by zirconocene dichloride [Cp2ZrCl2] has been studied. The reaction between [Cp2ZrCl2] and [Al(Oct)2H] in non-polar solvents leads to clusters containing bridging hydride ligands between Zr and Al. This system promotes hydroalumination of 1-octene but is largely ineffective for internal octenes (2-, 3-, 4-octene). In tetrahydrofuran the Zr–Al hydride clusters formed are more reactive and catalyse insertion and isomerisation of internal olefins to primary metal–alkyls, although this is accompanied by catalyst deactivation. Elimination and removal of 1-octene from the system post insertion/isomerisation was attempted, but it was found that the presence of the Zr catalyst leads to back-isomerisation to internal octenes, along with further decomposition with n-octane formation. Some possible pathways of catalyst decomposition, involving reduction of Zr and alkane elimination, have been studied theoretically.
Funding
Australian Research Council
History
Publication title
Dalton TransactionsVolume
44Issue
46Pagination
20098-20107ISSN
1477-9226Department/School
School of Natural SciencesPublisher
Royal Soc ChemistryPlace of publication
Thomas Graham House, Science Park, Milton Rd, Cambridge, England, Cambs, Cb4 0WfRights statement
Copyright 2015 The Royal Society of ChemistryRepository Status
- Restricted