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Type: Journal article
Title: The influence of N-substitution on the reductive elimination behaviour of hydrocarbyl-palladium-carbene complexes: a DFT study
Author: Graham, David Carl
Cavell, Kingsley J.
Yates, Brian F.
Citation: Dalton Transactions, 2006; 14:1768-1775
Publisher: Royal Society of Chemistry
Issue Date: 2006
ISSN: 1477-9226
School/Discipline: School of Chemistry and Physics : Chemistry
Statement of
David C. Graham, Kingsley J. Cavell and Brian F. Yates
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 p-orbital in determining the barrier to reductive elimination means N-substituents that are capable of removing -density (e.g. phenyl) act to promote a more facile reductive elimination.
Rights: © The Royal Society of Chemistry 2006
DOI: 10.1039/b512681a
Appears in Collections:Chemistry publications

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