%0 Journal Article %T Oxidative Addition of Haloheteroarenes to Palladium(0): Concerted versus S N Ar-Type Mechanism %+ department of chemistry %+ Processus d'Activation Sélective par Transfert d'Energie Uni-électronique ou Radiatif (UMR 8640) (PASTEUR) %+ Laboratoire de Chimie Moléculaire et de Catalyse pour l'Energie (ex LCCEF) (LCMCE) %A Maes, Bert U.W. %A Verbeeck, Stefan %A Verhelst, Tom %A Ekomié, Audrey %A Von wolff, Niklas %A Lefèvre, Guillaume %A Mitchell, Emily A. %A Jutand, Anny %< avec comité de lecture %@ 0947-6539 %J Chemistry - A European Journal %I Wiley-VCH Verlag %V 21 %N 21 %P 7858 - 7865 %8 2015-04-18 %D 2015 %R 10.1002/chem.201406210 %Z Chemical Sciences/Material chemistryJournal articles %X The kinetics of the oxidative additions of haloheteroarenes HetX (X=I, Br, Cl) to [Pd-0(PPh3)(2)] (generated from [Pd-0(PPh3)(4)]) have been investigated in THF and DMF and the rate constants have been determined. In contrast to the generally accepted concerted mechanism, Hammett plots obtained for substituted 2-halopyridines and solvent effects reveal a reaction mechanism dependent on the halide X of HetX: an unprecedented SNAr-type mechanism for X=Br or Cl and a classical concerted mechanism for X=I. These results are supported by DFT studies. %G English %L cea-01635498 %U https://cea.hal.science/cea-01635498 %~ CEA %~ ENS-PARIS %~ UPMC %~ CNRS %~ PASTEUR_UMR8640 %~ PUBNIMBE %~ INC-CNRS %~ IRAMIS-NIMBE %~ CEA-UPSAY %~ PSL %~ UNIV-PARIS-SACLAY %~ CEA-UPSAY-SACLAY %~ UPMC_POLE_2 %~ SORBONNE-UNIVERSITE %~ SU-SCIENCES %~ ENS-PSL %~ GS-ENGINEERING %~ IRAMIS %~ GS-CHIMIE %~ GS-PHYSIQUE %~ INSTITUT-SCIENCES-LUMIERE %~ ALLIANCE-SU %~ CHIMIE-SU