eCite Digital Repository

Insertion and isomerisation of internal olefins at alkylaluminium hydride: catalysis with zirconocene dichloride


Weliange, NM and McGuinness, DS and Gardiner, MG and Patel, J, Insertion and isomerisation of internal olefins at alkylaluminium hydride: catalysis with zirconocene dichloride, Dalton Transactions, 44, (46) pp. 20098-20107. ISSN 1477-9226 (2015) [Refereed Article]

Copyright Statement

Copyright 2015 The Royal Society of Chemistry

DOI: doi:10.1039/c5dt03257a


The 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.

Item Details

Item Type:Refereed Article
Keywords:olefin, catalysis
Research Division:Chemical Sciences
Research Group:Inorganic chemistry
Research Field:Organometallic chemistry
Objective Division:Manufacturing
Objective Group:Industrial chemicals and related products
Objective Field:Organic industrial chemicals (excl. resins, rubber and plastics)
UTAS Author:Weliange, NM (Dr Malathi Weliange)
UTAS Author:McGuinness, DS (Dr David McGuinness)
UTAS Author:Gardiner, MG (Associate Professor Michael Gardiner)
ID Code:105976
Year Published:2015
Funding Support:Australian Research Council (DP120101558)
Web of Science® Times Cited:5
Deposited By:Chemistry
Deposited On:2016-01-21
Last Modified:2018-03-14

Repository Staff Only: item control page