Synthesis and stereochemical studies of η3-allyl palladium(II) complexes containing a chiral chelating ligand

A complex of the type [Pd(η3-CH2CMeCH2)(P–P′)]+[where P–P′= the chiral chelating ligand (S-)–(N-diphenylphosphino)(2-diphenylphosphinoxymethyl) pyrrolidine, not having C2v symmetry] has been prepared and its 1H, 13C, 31P, and two-dimensional H–X (X =13C or 31P) correlation spectra recorded. On the basis of n.m.r. data the absolute configurations in solution of the major and minor diastereoisomers have been assigned. Proton and 13C n.m.r. data have been discussed in terms of trans influence of the chelating ligand P–P′. Correlations between the n.m.r. parameters of the intermediate η3-allyl diastereoisomers, donor properties of the ligand, and regiochemistry of nucleophilic addition to the allyl termini have been proposed.