Oxidative Addition of Haloheteroarenes to Palladium(0): Concerted versus S N Ar-Type Mechanism

Abstract : 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.
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Article dans une revue
Chemistry - A European Journal, Wiley-VCH Verlag, 2015, 21 (21), pp.7858 - 7865. 〈10.1002/chem.201406210〉
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https://hal-cea.archives-ouvertes.fr/cea-01635498
Contributeur : Serge Palacin <>
Soumis le : mercredi 15 novembre 2017 - 11:39:50
Dernière modification le : mercredi 21 mars 2018 - 18:57:17

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Bert U.W. Maes, Stefan Verbeeck, Tom Verhelst, Audrey Ekomié, Niklas Von wolff, et al.. Oxidative Addition of Haloheteroarenes to Palladium(0): Concerted versus S N Ar-Type Mechanism. Chemistry - A European Journal, Wiley-VCH Verlag, 2015, 21 (21), pp.7858 - 7865. 〈10.1002/chem.201406210〉. 〈cea-01635498〉

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