Oxidative Addition of Haloheteroarenes to Palladium(0): Concerted versus S N Ar-Type Mechanism - Archive ouverte HAL Access content directly
Journal Articles Chemistry - A European Journal Year : 2015

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

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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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cea-01635498 , version 1 (15-11-2017)

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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, 2015, 21 (21), pp.7858 - 7865. ⟨10.1002/chem.201406210⟩. ⟨cea-01635498⟩
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