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Insertion, elimination and isomerisation of olefins at alkylaluminium hydride: an experimental and theoretical study

Citation

Weliange, NM and McGuinness, DS and Gardiner, MG and Patel, J, Insertion, elimination and isomerisation of olefins at alkylaluminium hydride: an experimental and theoretical study, Dalton Transactions, 44, (34) pp. 15286-15296. ISSN 1477-9226 (2015) [Refereed Article]

Copyright Statement

Copyright 2015 The Royal Society of Chemistry

DOI: doi:10.1039/C5DT00955C

Abstract

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.

Item Details

Item Type:Refereed Article
Research Division:Chemical Sciences
Research Group:Inorganic Chemistry
Research Field:Transition Metal Chemistry
Objective Division:Manufacturing
Objective Group:Industrial Chemicals and Related Products
Objective Field:Organic Industrial Chemicals (excl. Resins, Rubber and Plastics)
Author:Weliange, NM (Dr Malathi Weliange)
Author:McGuinness, DS (Dr David McGuinness)
Author:Gardiner, MG (Associate Professor Michael Gardiner)
ID Code:102502
Year Published:2015
Web of Science® Times Cited:4
Deposited By:Chemistry
Deposited On:2015-08-25
Last Modified:2018-03-14
Downloads:0

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