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Modified [(IPr)Pd(R‐acac)Cl] Complexes: Influence of the acac Substitution on the Catalytic Activity in Aryl Amination
Author(s) -
Marion Nicolas,
Navarro Oscar,
Stevens Edwin D.,
Ecarnot Elise C.,
Bell Andrew,
Amoroso Dino,
Nolan Steven P.
Publication year - 2010
Publication title -
chemistry – an asian journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.18
H-Index - 106
eISSN - 1861-471X
pISSN - 1861-4728
DOI - 10.1002/asia.200900654
Subject(s) - chemistry , steric effects , amination , catalysis , ligand (biochemistry) , aryl , medicinal chemistry , palladium , stereochemistry , organic chemistry , receptor , biochemistry , alkyl
The synthesis of a series of [(IPr)Pd(R‐acac)Cl] precatalysts (acac=acetylacetonato; IPr=1,3‐bis(2,6‐diisopropylphenyl)imidazol‐2‐ylidene), where the acac ligand on palladium has been systematically modified through terminal substitution , is reported. The following substituted acac ligands are employed in this study: dibenzoylmethanato (dbm), benzoylacetonato (bac), tetramethylheptanedionato (tmhd), and hexafluoroacetylacetonato (hfac). Full spectroscopic characterization of the new complexes is provided along with X‐ray studies for three of these. Investigation of their catalytic activity in cross‐coupling is also presented through a comparative study in an aryl amination reaction. The catalytic results show a strong correlation between the increased steric bulk of the acac substituents and an increased activation rate of the precatalyst, going from the acac to the tmhd ligand. This observation, along with the inertness of the hfac compound, seems to support our previous proposal for the activation mechanism of these complexes under cross‐coupling conditions.