Density functional theory has been used to investigate various solvated species that may be formed from palladium bis N-heterocyclic carbene complexes, [Pd(cyclo-C{NRCH}2)2], (PdL2) in benzene solution. Formation of an η2-arene complex is shown to stabilise a monocarbene species, PdL(η2-C6H5X), where the arene is either the solvent or a reacting aryl halide. Oxidative addition of an aryl chloride has been modelled, and the most likely transition state has been established as a PdL(arylchloride) species, with just one carbene ligand coordinated to the palladium. The catalytic cycle for aryl amination has been investigated and the oxidative addition of the aryl halide shown to be the rate determining step. Reductive elimination of the aryl amine has a lower activation energy. Oxidative addition of alkyl halides has been shown to be less favourable because of the absence of an unsaturated group, such as the aryl ring, to bond to the palladium. © 2005 Elsevier B.V. All rights reserved.
