Self-Adaptable Catalysts: Substrate-Dependent Ligand Configuration

Pd(II) allyl and Pd(0) olefin complexes containing the configurationally labile ligand 1,2-bis-[4,5-dihydro-3H-dibenzo[c−e]azepino]ethane were studied as models for intermediates in Pd-catalyzed allylic
alkylations. According to NMR and DFT studies, the ligand prefers Cs conformation in both η3-1,3-diphenylpropenyl and η3-cyclohexenyl Pd(II) complexes, whereas in Pd(0) olefin complexes it adopts different
conformations in complexes derived from the two types of allyl systems in both solution and, as verified by
X-ray crystallography, in the solid state. These results demonstrate that the Pd complex is capable of
adapting its structure to the reacting substrate. The different structural preferences also provide an
explanation for the behavior of 1,3-diphenyl-2-propenyl acetate and 2-cyclohexenyl acetate in Pd-catalyzed
allylic alkylations using pseudo-C2 and pseudo-Cs symmetric ligands.