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Pure Appl. Chem., 2010, Vol. 82, No. 7, pp. 1393-1402

Published online 2010-05-04

Mechanism of the oxidative addition of aryl halides to bis-carbene palladium(0) complexes

Anny Jutand1*, Julien Pytkowicz2, Sylvain Roland2 and Pierre Mangeney2

1 Department of Chemistry, Ecole Normale Supérieure, UMR CNRS-ENS-UPMC 8640, 24 Rue Lhomond, F-75231, Paris Cedex 5, France
2 Paris Institute of Molecular Chemistry, UMR CNRS-UPMC 7201, Université Pierre et Marie Curie, Bât F, Pièce 665, BC 43, 4 Place Jussieu, F-75252, Paris Cedex 05, France

Abstract: Bis-N-heterocyclic carbenes Pd0 complexes, Pd0(NHC)2, are efficient catalysts in Heck reactions performed with aryl bromides or chlorides. The Pd0(NHC)2 that are not stable are generated in situ from PdII precursors PdY2(NHC)2 (Y = halides) after a chemical reduction. The latter procedure can be mimicked by an electrochemical reduction. The transient Pd0(NHCBn)2 is generated by electrochemical reduction of PdY2(NHCBn)2, and its reactivity in oxidative addition to aryl bromides and chlorides is characterized by the same electrochemical technique with the determination of the rate constants. Pd0(NHCBn)2 is found to be more reactive than the mixed complex Pd0(NHCBn)(PPh3). Both are the reactive species in an associative mechanism. Comparison with the isolated Pd0(NHCtBu)2 reveals that Pd0(NHCBn)2 is more reactive than Pd0(NHCtBu)2 even if the latter reacts via the mono-carbene Pd0(NHCtBu) in a dissociative mechanism. This suggests that the formation of mono-carbene Pd0(NHC) is not a guarantee for a fast oxidative addition because it is always generated at low concentration in its equilibrium with the related nonreactive bis‑carbene Pd0(NHC)2.