Premium
Catalyst Activation, Deactivation, and Degradation in Palladium‐Mediated Negishi Cross‐Coupling Reactions
Author(s) -
Böck Katharina,
Feil Julia E.,
Karaghiosoff Konstantin,
Koszinowski Konrad
Publication year - 2015
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201406408
Subject(s) - chemistry , catalysis , negishi coupling , reagent , palladium , reactivity (psychology) , coupling reaction , aryl , photochemistry , substrate (aquarium) , ligand (biochemistry) , electrospray ionization , context (archaeology) , oxidative addition , inorganic chemistry , medicinal chemistry , organic chemistry , ion , alkyl , paleontology , biochemistry , medicine , alternative medicine , oceanography , receptor , pathology , biology , geology
Pd‐mediated Negishi cross‐coupling reactions were studied by a combination of kinetic measurements, electrospray‐ionization (ESI) mass spectrometry, 31 P NMR and UV/Vis spectroscopy. The kinetic measurements point to a rate‐determining oxidative addition. Surprisingly, this step seems to involve not only the Pd catalyst and the aryl halide substrate, but also the organozinc reagent. In this context, the ESI‐mass spectrometric observation of heterobimetallic Pd–Zn complexes [L 2 PdZnR] + (L=S‐PHOS, R=Bu, Ph, Bn) is particularly revealing. The inferred presence of these and related neutral complexes with a direct Pd–Zn interaction in solution explains how the organozinc reagent can modulate the reactivity of the Pd catalyst. Previous theoretical calculations by González‐Pérez et al. ( Organometallics 2012 , 31 , 2053) suggest that the complexation by the organozinc reagent lowers the activity of the Pd catalyst. Presumably, a similar effect also causes the rate decrease observed upon addition of ZnBr 2 . In contrast, added LiBr apparently counteracts the formation of Pd–Zn complexes and restores the high activity of the Pd catalyst. At longer reaction times, deactivation processes due to degradation of the S‐PHOS ligand and aggregation of the Pd catalyst come into play, thus further contributing to the appreciable complexity of the title reaction.