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The influence of N-substitution on the reductive elimination behaviour of hydrocarbyl-palladium-carbene complexes-a DFT study
Citation
Graham, DC and Cavell, KJ and Yates, BF, The influence of N-substitution on the reductive elimination behaviour of hydrocarbyl-palladium-carbene complexes-a DFT study, Dalton Transactions, 6, (14) pp. 1768-1775. ISSN 1477-9226 (2006) [Refereed Article]
DOI: doi:10.1039/b512681a
Abstract
The reductive elimination of 2-hydrocarbyl-imidazolium salts from hydrocarbyl-palladium complexes bearing N-heterocyclic carbene (NHC) ligands represents an important deactivation route for catalysts of this type. We have explored the influence that carbene N-substituents have on both the activation energy and the overall thermodynamics of the reductive elimination reaction using density functional theory (DFT). Given the proximity of the N-substituent to the three-centred transition structure, steric bulk has little influence on the activation barrier and it is electronic factors that dominate the barriers' magnitude. Increased electron donation from the departing NHC ligand acts to stabilise the associated complex against reductive elimination, with stability following the trend: Cl < H < Ph < Me < Cy < iPr < neopentyl < tBu. The intimate involvement of the carbene pπ-orbital in determining the barrier to reductive elimination means N-substituents that are capable of removing π-density (e.g. phenyl) act to promote a more facile reductive elimination. © The Royal Society of Chemistry 2006.
Item Details
Item Type: | Refereed Article |
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Research Division: | Chemical Sciences |
Research Group: | Inorganic chemistry |
Research Field: | Organometallic 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: | 43154 |
Year Published: | 2006 |
Web of Science® Times Cited: | 55 |
Deposited By: | Chemistry |
Deposited On: | 2006-08-01 |
Last Modified: | 2012-03-05 |
Downloads: | 0 |
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