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Reductive Eliminations from Diarylpalladium(II) Complexes: A Combined Experimental and Computational Investigation
Author(s) -
Gensch Tobias,
Thoran Robert,
Richter Nils,
Knölker HansJoachim
Publication year - 2017
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.201702773
Subject(s) - reductive elimination , chemistry , ligand (biochemistry) , triphenylphosphine , regioselectivity , palladium , combinatorial chemistry , elimination reaction , computational chemistry , medicinal chemistry , organic chemistry , catalysis , receptor , biochemistry
The diverse mechanisms for the reductive elimination of biaryl compounds from diarylpalladium(II) complexes with a tetradentate ligand were investigated through a combined experimental and computational study. At least four distinct chemical triggers with specific regioselectivity exist for this elimination. Heating of the complexes in inert solvents (e.g., para ‐xylene) reveals their relatively high thermal stability as reflected by a very high barrier for a unimolecular reductive elimination. In contrast, electron‐donor ligands like triphenylphosphine induce a facile reductive elimination via twofold associative ligand exchange as confirmed by kinetic experiments, which are in good agreement with the computational results. Oxidants, such as H 2 O 2 , can trigger an oxidation‐induced reductive elimination via palladium(IV) intermediates at room temperature. Rearrangement of the diarylpalladium(II) complexes can occur in organic acids, facilitating a reductive elimination with distinct regiochemical outcome.