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Theoretical evaluation of alternative pathways in the Stevens rearrangement
Citation
Heard, GL and Yates, BF, Theoretical evaluation of alternative pathways in the Stevens rearrangement, Australian Journal of Chemistry, 48, (8) pp. 1413-1423. ISSN 0004-9425 (1995) [Refereed Article]
Abstract
Ab initio and semi-empirical molecular orbital theory has been used to explore the ion-pair and lithium-catalysed pathways in the Stevens rearrangement of an alkylammonium ylide to an amine. These pathways represent alternatives to the concerted and free radical mechanisms which we have previously studied. Solvation effects have been included via a polarizable continuum model. Finally, the calculations have been extended to a set of experimentally observable compounds. For the nine systems studied here, the stepwise free radical pathway is predicted in every case to be the favourable mechanism for the Stevens rearrangement. Single-point MP2/6-31G(d) calculations on fully optimized PM3 geometries are shown to provide a useful method of including electron correlation at low computational cost. © 1995 ASEG.
Item Details
Item Type: | Refereed Article |
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Research Division: | Chemical Sciences |
Research Group: | Theoretical and Computational Chemistry |
Research Field: | Theoretical and Computational Chemistry not elsewhere classified |
Objective Division: | Expanding Knowledge |
Objective Group: | Expanding Knowledge |
Objective Field: | Expanding Knowledge in the Chemical Sciences |
UTAS Author: | Heard, GL (Mr George Lance Heard) |
UTAS Author: | Yates, BF (Professor Brian Yates) |
ID Code: | 4596 |
Year Published: | 1995 |
Web of Science® Times Cited: | 12 |
Deposited By: | Chemistry |
Deposited On: | 1995-08-01 |
Last Modified: | 2011-08-24 |
Downloads: | 0 |
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