title: Insertion and isomerisation of internal olefins at alkylaluminium hydride: catalysis with zirconocene dichloride.
abstract: 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.
authors.affiliation: School of Physical Sciences - Chemistry, Private Bag 75, Hobart 7001, Australia. david.mcguinness@utas.edu.au.
authors.forename: Nandita M
authors.initials: NM
authors.lastname: Weliange
authors.affiliation: School of Physical Sciences - Chemistry, Private Bag 75, Hobart 7001, Australia. david.mcguinness@utas.edu.au.
authors.forename: David S
authors.initials: DS
authors.lastname: McGuinness
authors.affiliation: School of Physical Sciences - Chemistry, Private Bag 75, Hobart 7001, Australia. david.mcguinness@utas.edu.au.
authors.forename: Michael G
authors.initials: MG
authors.lastname: Gardiner
authors.affiliation: CSIRO Energy, 71 Normanby Rd, Clayton North 3169, Australia.
authors.forename: Jim
authors.initials: J
authors.lastname: Patel