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Dimerization mechanisms of heterocyclic carbenes

journal contribution
posted on 2023-05-16, 17:11 authored by Graham, DC, Cavell, KJ, Brian YatesBrian Yates
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.

History

Publication title

Journal of Physical Organic Chemistry

Volume

18

Issue

4

Pagination

298-309

ISSN

0894-3230

Department/School

School of Natural Sciences

Publisher

John Wiley & Sons Ltd

Place of publication

Chichester

Repository Status

  • Restricted

Socio-economic Objectives

Expanding knowledge in the chemical sciences

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