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Updated: Aug 19, 2026

Palladium N-Heterocyclic Carbene Complexes: Synthesis from Benzimidazolium Salts and Catalytic Activity in Carbon-carbon Bond-forming Reactions
Published on: July 30, 2017
Influence of geometry on reductive elimination of hydrocarbyl-palladium-carbene complexes
David C Graham1, Kingsley J Cavell, Brian F Yates
1School of Chemistry, University of Tasmania, Private Bag 75, Hobart, Tasmania 7001, Australia.
Abstract:
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 (E(act)) and the enthalpy of reaction. Widening of the bite angle was found to lower E(act) and increase the enthalpy of reaction. In contrast, rotation of the carbene with respect to the PdL(2) plane was found to have little influence on E(act). At carbene twist angles approaching 0 degrees however, relief of the increased steric strain provides a considerable driving force for the decomposition reaction.
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