RESUMO
Free energy barriers to biaryl tropoinversion in metal complexes with tropos phosphepine and azepine ligands were determined by temperature-dependent (31)P NMR inversion-transfer experiments and line shape analysis of the temperature-dependent (1)H NMR spectra, respectively. The barrier in the PdCl(2) complex of the azepine ligand was found to be slightly higher than that of the corresponding free ligand. Studies of a tridentate azepine ligand suggested that configurational change takes place without prior decoordination from the metal.
RESUMO
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(s) conformation in both eta3-1,3-diphenylpropenyl and eta3-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.