37167-65-0Relevant academic research and scientific papers
Insertion and isomerisation of internal olefins at alkylaluminium hydride: Catalysis with zirconocene dichloride
Weliange, Nandita M.,McGuinness, David S.,Gardiner, Michael G.,Patel, Jim
, p. 20098 - 20107 (2015/12/01)
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.
Insertion, elimination and isomerisation of olefins at alkylaluminium hydride: An experimental and theoretical study
Weliange, Nandita M.,McGuinness, David S.,Gardiner, Michael G.,Patel, Jim
, p. 15286 - 15296 (2015/09/01)
The insertion, elimination and isomerisation of octenes with di-n-octylaluminium hydride [HAl(Oct)2], tri-n-octylaluminium [Al(Oct)3] and sec-octylaluminium species have been studied as individual steps in a putative aluminium based contrathermodynamic olefin isomerisation process. While elimination of 1-octene from [Al(Oct)3] is energetically unfavourable, the process is driven by high temperature vacuum distillation, leading to very high selectivity to 1-octene (>97%). At high conversions the [HAl(Oct)2] so obtained exists predominately as hydride-bridged cyclic oligomers, whereas at low conversion the mixed alkyl/hydride-bridged dimer [(Oct)2Al(μ-H)(μ-Oct)Al(Oct)2] is the major species. Di-n-octylaluminium hydride recovered after olefin elimination may be recycled and is active toward re-insertion of octenes. Internal octenes (cis- and trans-2-, 3- and 4-octene) only partially insert however, and even after prolonged heating there is no significant secondary to primary alkyl isomerisation evident.
One-step synthesis of trialkylaluminum derivatives and dialkylaluminum hydrides by the reaction of alkaline metal aluminum hydrides with α-olefins and alkylaluminum chlorides
Gavrilenko
, p. 168 - 169 (2007/10/03)
A simple method for one-step preparation of the organoaluminum compounds R3Al, R2AlH, R2R′Al, and RR′AlH by the reaction of MAlH4 (M = Li, Na) with R2AlHal (Hal = Cl, Br) and α-olefins (3-methylbut-1-ene, hex-1-ene, oct-1-ene, dec-1-ene) was proposed.
