98. Self-Adaptable Catalysts: Substrate Dependent Ligand Configuration
    Raivis Zalubovskis, Alexis Bouet, Ester Fjellander, Samuel Constant, David Linder, Andreas Fischer, Jérôme Lacour, Timofei Privalov, Christina Moberg
    J. Am. Chem. Soc. 2008, 130, 1845-1855

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 C_sconformation 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-C_s symmetric ligands.

DOI : 10.1021/ja074044k 

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