The influence of spectator ligand bite angle and the twist angle of the carbene on the reductive elimination of N-heterocyclic carbenes (NHCs) from palladium bis-phosphine complexes has been investigated using density functional theory. The spectator bite angle was found to have a significant influence on both the activation energy (Eact) and the enthalpy of reaction. Widening of the bite angle was found to lower Eact and increase the enthalpy of reaction. In contrast, rotation of the carbene with respect to the PdL2 plane was found to have little influence on EEact. At carbene twist angles approaching 0° however, relief of the increased steric strain provides a considerable driving force for the decomposition reaction. © The Royal Society of Chemistry 2005.

Item Type:	Refereed Article
Research Division:	Chemical Sciences
Research Group:	Inorganic Chemistry
Research Field:	Transition Metal Chemistry
Objective Division:	Expanding Knowledge
Objective Group:	Expanding Knowledge
Objective Field:	Expanding Knowledge in the Chemical Sciences
Author:	Graham, DC (Dr David Graham)
Author:	Cavell, KJ (Professor Kingsley Cavell)
Author:	Yates, BF (Professor Brian Yates)
ID Code:	36393
Year Published:	2005
Web of Science® Times Cited:	38
Deposited By:	Chemistry
Deposited On:	2005-08-01
Last Modified:	2012-03-05
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