eCite Digital Repository

Thermal dehydroboration: experimental and theoretical studies of olefin elimination from trialkylboranes and its relationship to alkylborane isomerization and transalkylation

Citation

Weliange, NM and McGuinness, DS and Patel, J, Thermal dehydroboration: experimental and theoretical studies of olefin elimination from trialkylboranes and its relationship to alkylborane isomerization and transalkylation, Organometallics, 33, (16) pp. 4251-4259. ISSN 0276-7333 (2014) [Refereed Article]

Copyright Statement

Copyright 2014 American Chemical Society

DOI: doi:10.1021/om5005397

Abstract

The thermal elimination of α-olefin from tri-n-alkylborane (dehydroboration) has been studied both experimentally and theoretically. High-temperature 1H NMR spectroscopy and temperature quench experiments revealed no evidence for practically significant concentrations of free olefin at temperatures up to 200 C. Furthermore, attempts to remove 1-octene from tri-n-octylborane by prolonged heating under vacuum were largely unsuccessful. The experimental findings were supported by high-level theoretical calculations, which predicted a very minor equilibrium concentration of dehydroboration products at temperatures less than 200 C. The results revealed that a putative continuous dehydroboration process will most likely be a slow process and will be difficult to achieve selectively. At the same time, reversible dehydroboration was found to be the most likely route for alkylborane isomerization and transalkylation reactions, and theoretical findings were used to rationalize previous experimental findings. A range of alternative mechanistic proposals for isomerization and transalkylation were also evaluated and were found to be uncompetitive with dehydroboration.

Item Details

Item Type:Refereed Article
Keywords:isomerization, alpha-olefins, catalysis
Research Division:Chemical Sciences
Research Group:Other Chemical Sciences
Research Field:Organometallic 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)
ID Code:97338
Year Published:2014
Funding Support:Australian Research Council (DP120101558)
Web of Science® Times Cited:7
Deposited By:Chemistry
Deposited On:2014-12-11
Last Modified:2015-04-28
Downloads:0

Repository Staff Only: item control page