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Self-adaptable catalysts : substrate-dependent ligand configuration

Zalubovskis, Raivis
Bouet, Alexis
Fjellander, Ester
Constant, Samuel
Fischer, Andreas
Privalov, Timofei
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Published in Journal of the American Chemical Society. 2008, vol. 130, no. 6, p. 1845-1855
Abstract 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 3-1,3-diphenylpropenyl and 3-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.
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ZALUBOVSKIS, Raivis et al. Self-adaptable catalysts : substrate-dependent ligand configuration. In: Journal of the American Chemical Society, 2008, vol. 130, n° 6, p. 1845-1855. doi: 10.1021/ja074044k https://archive-ouverte.unige.ch/unige:45

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Deposited on : 2008-10-29

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