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Dimerization mechanisms of heterocyclic carbenes
Citation
Graham, DC and Cavell, KJ and Yates, BF, Dimerization mechanisms of heterocyclic carbenes, Journal of Physical Organic Chemistry, 18, (4) pp. 298-309. ISSN 0894-3230 (2005) [Refereed Article]
DOI: doi:10.1002/poc.846
Abstract
The dimerization reactions of a series of heterocyclic carbenes based on the 1,3-dimethylimidazol-2-ylidene template were studied extensively using molecular orbital calculations. The carbenes studied were the 1,3-XY five-membered ring heterocyclic carbenes with all 10 possible combinations of X,Y = NCH3, PCH3, O and S. Two different mechanisms for dimerization were studied: a direct carbene plus carbene dimerization reaction and a proton-catalysed dimerization. The parent carbene with XY = NN is found to be kinetically and thermodynamically stable under both mechanisms, whereas XY = NS is predicted to be kinetically stable under aprotic conditions. All remaining carbenes were predicted to be not particularly stable towards dimerization. Indirect schemes for calculating the stability of carbenes towards dimerization were found to give good estimates of the enthalpy of dimerization, but do not take into account the activation barriers. Copyright ©2004 John Wiley & Sons, Ltd.
Item Details
Item Type: | Refereed Article |
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Research Division: | Chemical Sciences |
Research Group: | Organic chemistry |
Research Field: | Physical organic chemistry |
Objective Division: | Expanding Knowledge |
Objective Group: | Expanding knowledge |
Objective Field: | Expanding knowledge in the chemical sciences |
UTAS Author: | Graham, DC (Dr David Graham) |
UTAS Author: | Cavell, KJ (Professor Kingsley Cavell) |
UTAS Author: | Yates, BF (Professor Brian Yates) |
ID Code: | 36391 |
Year Published: | 2005 |
Web of Science® Times Cited: | 40 |
Deposited By: | Chemistry |
Deposited On: | 2005-08-01 |
Last Modified: | 2006-04-03 |
Downloads: | 0 |
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