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Detailed analysis of the parameters of the 1H NMR spectra and X-ray diffraction data was performed for a series of the adducts of chiral α-arylalkylaminate palladacycles with P-donors including dozens of previously prepared or known complexes with achiral or P*-chiral phosphine or phosphite auxilliary ligands. It was shown that the configuration of the asymmetric α-arylalkylaminate carbon atom defines the stereochemistry of the twisted palladacycle and of the tetrahedrally distorted coordination environment of the metal.